US5449809A - Acetylene derivatives and crop protection agents containing them - Google Patents
Acetylene derivatives and crop protection agents containing them Download PDFInfo
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- US5449809A US5449809A US08/099,693 US9969393A US5449809A US 5449809 A US5449809 A US 5449809A US 9969393 A US9969393 A US 9969393A US 5449809 A US5449809 A US 5449809A
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- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/23—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same unsaturated acyclic carbon skeleton
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- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
Definitions
- the present invention relates to novel acetylene derivatives and a method for controlling pests, in particular fungi, insects, nematodes and spider mites, with these compounds.
- U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
- A is C 1 -C 4 -alkylidene, C 1 -C 4 -alkoxymethylidene, C 1 -C 4 -alkylthiomethylidene or C 1 -C 4 -alkoximino,
- B is OH, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylamino
- R is hydrogen, halogen, cyano, CF 3 , straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 6 -cycloalkyl, unsubstituted or substituted aryl, halo-C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 4 -alkynyl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted hetaryl, unsubstituted or substituted aryl-C 1 -C 4 -alkyl, unsubstituted or substituted aryl-C 2 -C 4 -alkenyl, unsubstituted or substituted arylethynyl, unsubstituted or substituted hetaryl-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl
- R 1 -R 17 , R 19 and R 20 are identical or different and are each hydrogen, C 1 -C 4 -alkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted hetarylalkyl,
- R 18 is OH, C 1 -C 4 -alkoxy or unsubstituted or substituted aryl-C 1 -C 4 -alkoxy, the term "unsubstituted or substituted” denoting, in addition to hydrogen, the substitutents halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkoximino-C 1 -C 4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C 3 -C 6 -cycloalkyl, C 1 -C 4 -dialkylamino, CO 2 Me, CO 2 Et, formyl and acyl, Me being methyl, Et being ethyl and the expression het
- A is CHOCH 3
- B is OCH 3 and R is phenyl
- A is CHSCH 3
- B is OCH 3 and R is phenyl
- A is CHCH 3
- B is OCH 3 and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
- A is NOCH 3
- B is OCH 3 and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
- A is NOCH 3
- B is NHCH 3 or R is CH 3 or phenyl
- A is CHOCH 3
- B is NHCH 3 and R is CH 3 or phenyl and
- A is CHSCH 3
- B is NHCH 3
- R is phenyl
- the fungicidal and insecticidal activity is preferred.
- U, V and W may each be hydrogen, halogen (e.g. fluorine, chlorine, bromine or iodine), methyl or methoxy,
- halogen e.g. fluorine, chlorine, bromine or iodine
- A may be C 1 -C 4 -alkylidene (e.g. methylidene, ethylidene, n-propylidene, isopropylidene, n-butylidene, isobutylidene, sec-butylidene or tert-butylidene), C 1 -C 4 -alkoxymethylidene t(e.g. methoxy-, ethoxy-, n-propoxy-, iso-propoxy-, n-butoxy-, isobutoxy-, sec-butoxy- or tert-butoxymethylidene), C 1 -C 4 -alkylthiomethylidene (e.g.
- C 1 -C 4 -alkoximino e.g. methoximino, ethoximino, n-propoximino, isopropoximino, n-butoximino, isobutoximino, sec-butoximino or tert-butoximino
- C 1 -C 4 -alkoximino e.g. methoximino, ethoximino, n-propoximino, isopropoximino, n-butoximino, isobutoximino, sec-butoximino or tert-butoximino
- B may be OH, C 1 -C 4 -alkoxy (e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy) or C 1 -C 4 -alkylamine (e.g. methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine or tert-butylamine), and
- R is hydrogen, halogen (fluorine, chlorine, bromine or iodine), cyano, CF 3 straight-chain or branched C 1 -C 10 -alkyl (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl or n-decyl), C 3 -C 6 -cycloalkyl (e.g.
- cyclopropyl cyclobutyl, cyclopentyl or cyclohexyl
- unsubstituted or substituted aryl e.g. phenyl, naphthyl or anthryl
- halo-C 1 -C 4 -alkyl e.g. bromomethyl, chloromethyl, iodomethyl or CF 3 -methyl
- C 2 -C 6 -alkenyl e.g.
- oxiranyl 1-aziridinyl, 1-azetidinyl, 1-pyrrolidinyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 1-piperidinyl, 1-morpholinyl, 1-piperazinyl, 1,3-dioxanyl, 3-tetrahydrothiopyranyl), unsubstituted or substituted hetaryl (e.g.
- pyridyl 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl, 2-benzothiazolyl), unsubstituted or substituted aryl-C 2 -C 4 -alkyl (e.g.
- benzyl 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-methyl-3-phenylpropyl, 2-methyl-2-phenylpropyl or 4-phenylbutyl), unsubstituted or substituted aryl-C 1 -C 4 -alkenyl (e.g. phenyl-1-ethenyl, 2-phenyl-1-propenyl, 2,2-diphenylethenyl, 1-phenyl-1-propen-2-yl or 1-phenyl-1-ethenyl), unsubstituted or substituted arylethynyl (e.g.
- phenylethynyl unsubstituted or substituted hetaryl-C 1 -C 4 -alkyl (e.g. pyridylmethyl or 3-pyridylmethyl), C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl (e.g.
- phenoxymethyl unsubstituted or substituted hetaryloxy-C 1 -C 4 -alkyl (e.g. 2-thienyloxymethyl), unsubstituted or substituted arylamino-C 1 -C 4 -alkyl (e.g. N-(phenylamino)-methyl), C(O)R 1 (e.g. C(O)CH 3 , C(O)CH 2 CH 3 or C(O)phenyl), C(O)NR 2 R 3 (e.g. C(O)NH 2 , C(O)NHCH 3 ), C(S)NR 2 R 3 (e.g.
- C(O)R 1 e.g. C(O)CH 3 , C(O)CH 2 CH 3 or C(O)phenyl
- C(O)NR 2 R 3 e.g. C(O)NH 2 , C(O)NHCH 3
- C(S)NR 2 R 3 e.g.
- C(O)SR 6 e.g. C(O)SCH 3 or C(O)SCH
- R 1 -R 17 , R 19 and R 20 are, for example, hydrogen C 1 -C 4 -alkyl (e.g. methyl, ethyl, n- and isopropyl, n-, iso-, sec- and tert-butyl), unsubstituted or substituted aryl (e.g. 2-chlorophenyl, 3,5-dimethylphenyl and 1-methyl-2-naphthyl), unsubstituted or substituted hetaryl (e.g.
- arylalkyl e.g. 2-chlorobenzyl and 3,5-dichlorobenzyl
- hetarylalkyl e.g. 2-furylmethyl and 6-methyl-2-pyridylmethyl
- R 18 is,
- radicals defined above as unsubstituted or substituted contain as substituents, apart from hydrogen, for example fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methoximinomethyl, ethoximinomethyl, n-propoximinomethyl, n-butoximinomethyl, n-pentoximinomethyl, n-hexyloximinomethyl, allyloximinomethyl, benzyloximinomethyl, isopropoximinomethyl, isobutoximinomethyl, tert-butoximinomethyl, methylimino-1-ethyl, ethoximino-1-e
- A is ethylidene, methoxymethylidene or methoximino
- B is methoxy or methylamine
- R has the abovementioned meanings, are preferred.
- the novel compounds of the general formula I may be obtained in the preparation as E/Z isomer mixtures. These can be separated into the individual components in a conventional manner, for example by crystallization or chromatography. Both the individual isomeric compounds and mixtures thereof form subjects of the invention and can be used as pesticides.
- novel compounds of the general formula I can be prepared by reacting, for example, an o-bromo compound 2 with a terminal acetylene derivative 3 in the presence of a transition metal catalyst, preferably a palladium compound, e.g. Pd(PPh 3 ) 4 , PdCl 2 or Pd(OAc) 2 , in the presence of triphenylphosphine and in the presence of a base, for example an N-alkylamine, such as triethylamine, and in the presence or absence of a solvent or diluent, e.g. dimethylformamide or acetonitrile (cf. for example L. Brandsma et al., Synth. Comm. 20 (1990), 1889 and W. B. Austin et al., J. Org. Chem. 46 (1981), 2280).
- a transition metal catalyst preferably a palladium compound, e.g. Pd(PPh 3 ) 4 , PdCl 2
- A, B, R, U, V and W have the meanings stated in claim 1.
- a catalyst e.g. PdCl 2 , Pd(OAc) 2 or Pd(PPh 3 ) 4
- a base such as triethylamine
- A, B, R, U, V and W have the meanings stated in claim 1.
- the ⁇ -keto acid derivatives of the terminal acetylenes 11 can be converted with the halides 10 under transition metal ##STR8## (TM)-catalysis into the derivatives 5, and the latter can be converted as described above into the novel compounds of the formula 1. ##STR9##
- the acetylene group in formula 12 is first produced by a known method (cf. for example Houben-Weyl, Vol. V/2a, page 33 et seq. (Viehe) or see Schemes 1+2) ##STR10## and the group Y is then converted into the group ##STR11##
- ketocarboxylic esters 17 can be prepared starting from the o-bromobenzaldehydes 13. ##STR12##
- the o-bromobenzaldehydes 12 can be reacted with the terminal acetylenes 3 under transition metal catalysis to give the aldehydes 14 (cf. W. B. Austin, J. Org. Chem. 46 (1981), 2280).
- the cyanohydrins 15 are obtained from the aldehydes 14 by reaction with a metal cyanide, such as NaCN or KCN, in the presence of an acid, e.g. hydrochloric acid (cf. for example Organikum, 16th Edition, page 445 (1986)).
- a metal cyanide such as NaCN or KCN
- an acid e.g. hydrochloric acid (cf. for example Organikum, 16th Edition, page 445 (1986)).
- the mandelic acid derivatives 16 can be prepared from the cyanohydrins 15 via a Pinner reaction (cf., for example, Org. Synth. Coll. 4 (1963), 58).
- Oxidation of the mandelic acid derivatives 16, for example with a chromium compound, such as chromium trioxide, with sodium hypochlorite or with TEMPO gives the ⁇ -ketoesters 17 (cf. for example Houben-Weyl, Vol. 4/lb, pages 425-464 (1975); TEMPO tetramethylpiperidin-1-oxyl).
- novel compounds of the formula 1a in which A, U, V, W and R have the meanings stated in claim 1 and B is CO 2 Me, can be prepared from the ketoesters 17, as shown in Schemes 3 and 4.
- the ⁇ -ketocarboxylic esters 17 can be synthesized starting from the halogen derivatives 18, by Grignard reaction with oxalic acid compounds 19 similarly to Scheme 8 (cf., for example, J. S. Nimitz, J. Org. Chem. 46 (1981), 211). ##STR13##
- carboxylic acids 20 are converted via the stage of the acyl chlorides into the cyanides 21 and the latter are converted into the ketoesters 17 by a Pinner reaction.
- ##STR14## (cf. for example Organikum, 16th Edition, 423 et seq. (1986) and Angew. Chem. 94 (1982), 1).
- novel compounds of the formula 1 where A, X, Y, Z and R have the meanings stated in claim 1 and B is hydroxyl or alkylamino can be prepared from the carboxylic ester derivatives 1a. ##STR15##
- the carboxylic acids 22 are obtained by hydrolysis by known methods (cf. Organikum, 16th Edition, page 415 et seq. and page 622 (1986)).
- the amides 24 are either obtained from these in a conventional manner (Organikum, 16th Edition, page 412 (1986)) or alternatively from the carboxylic esters 1a directly by aminolysis with amines.
- novel compounds of the general formula I can also be prepared by converting a suitably substituted styryl compound 25 in a conventional manner into the corresponding acetylene derivative 1.
- X is H and Y is halogen or X is halogen and Y is H
- the cleavage can be carried out with zinc (cf. for example H. G. Viehe, Chemistry of Acetylenes, Marcel Dekker, New York, 1969, page 134 et seq.).
- novel compounds are suitable as fungicides.
- the fungicidal compounds according to the invention may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering.
- the forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
- the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.
- the formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents.
- auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.
- solvents such as aromatics (e.g.,
- surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxy
- Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
- Granules e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers.
- solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
- mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatom
- V A hammer-milled mixture of 80 parts by weight of compound no. 31 from Table 2, 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.
- IX A stable oily dispersion of 20 parts by weight of compound no. 42 from Table 2, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
- novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a remarkably high systemic mobility and action after application to the soil and particularly to foliage.
- the fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
- the compounds are applied by treating the seeds, plants, materials or soil to be protected against fungus attack with a fungicidally effective amount of the active ingredients.
- the compounds may be applied before or after infection of the materials, plants or seeds by the fungi.
- the compounds I are particularly useful for controlling the following plant diseases:
- Botrytis cinerea (gray mold) in strawberries and grapes
- novel compounds may also be used for protecting materials (timber), for example against Paecilomyces variotii.
- the fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient.
- the application rates depend on the type of effect desired, but are generally from 0.02 to 3 kg of active ingredient per hectare.
- agents according to the invention when used as fungicides, they may be employed together with other active ingredients, e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers.
- active ingredients e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers.
- Slices of green paprika pods were sprayed to runoff with aqueous formulations containing 80% of active ingredient and 20% of emulsifier. Two hours after the sprayed-on layer had dried, the slices were inoculated with a spore suspension of Botrytis cinerea containing 1.7 ⁇ 10 6 spores per ml of a 2% biomalt solution. The inoculated slices were then incubated in moist chambers for 4 days at 18° C. The extent of Botrytis spread on the slices was then assessed visually.
- Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24° C. and then in a greenhouse for 5 days at from 20° to 30° C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
Abstract
Acetylene derivatives of the general formula I ##STR1## where U, V and W are hydrogen, halogen, nitro, cyano, alkyl or alkoxy,
A is alkylidene, alkoxymethylidene, alkylthiomethylidene or alkoximino,
B is OH, alkoxy or alkylamino and
R is hydrogen, halogen, cyano, CF3, alkyl, cycloalkyl, haloalkyl, aryl, alkenyl, alkynyl, heterocyclyl, hetaryl, arylalkyl, arylalkenyl, arylethynyl, hetaryl-C1 -C4 -alkyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, aryloxyalkyl, hetaryloxyalkyl, arylamino-alkyl, arylthiomethyl, hetarylthiomethyl, C(O)R1, C(O)NR2 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, SiR12 R13 R14, SnR15 R16 R17, C(OR)R18 or C(═N--OR19)R20 and
R1 -R17, R19 and R20 are hydrogen, alkyl, aryl, hetaryl, arylalkyl or hetarylalkyl and R18 is OH, C1 -C4 -alkoxy or aryl-C1 -C4 -alkoxy, and fungicides containing these compounds.
Description
The present invention relates to novel acetylene derivatives and a method for controlling pests, in particular fungi, insects, nematodes and spider mites, with these compounds.
It is known that individual acetylene derivatives (European Patents 178,826, 244,077, 253,213, 280,185 and 477,631) have fungicidal or insecticidal activity. However, their activity is unsatisfactory.
We have found, surprisingly, that the novel acetylene derivatives of the general formula I ##STR2## where
U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C1 -C4 -alkyl or C1 -C4 -alkoxy,
A is C1 -C4 -alkylidene, C1 -C4 -alkoxymethylidene, C1 -C4 -alkylthiomethylidene or C1 -C4 -alkoximino,
B is OH, C1 -C4 -alkoxy or C1 -C4 -alkylamino, and
R is hydrogen, halogen, cyano, CF3, straight-chain or branched C1 -C10 -alkyl, C3 -C6 -cycloalkyl, unsubstituted or substituted aryl, halo-C1 -C4 -alkyl, C2 -C6 -alkenyl, C2 -C4 -alkynyl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted hetaryl, unsubstituted or substituted aryl-C1 -C4 -alkyl, unsubstituted or substituted aryl-C2 -C4 -alkenyl, unsubstituted or substituted arylethynyl, unsubstituted or substituted hetaryl-C1 -C4 -alkyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, unsubstituted or substituted aryloxy-C1 -C4 -alkyl, unsubstituted or substituted hetaryloxy-C1 -C4 -alkyl, unsubstituted or substituted arylamino-C1 -C4 -alkyl, unsubstituted or substituted arylthiomethyl, unsubstituted or substituted hetarylthiomethyl, C(O)R1, C(O)NR2 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, SiR12 R13 R14, SnR15 R16 R17, C(O)R18 or C(═N--OR19)R20 and
R1 -R17, R19 and R20 are identical or different and are each hydrogen, C1 -C4 -alkyl, unsubstituted or substituted aryl, unsubstituted or substituted hetaryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted hetarylalkyl,
R18 is OH, C1 -C4 -alkoxy or unsubstituted or substituted aryl-C1 -C4 -alkoxy, the term "unsubstituted or substituted" denoting, in addition to hydrogen, the substitutents halogen, cyano, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkyl, C1 -C4 -haloalkoxy, C1 -C4 -alkoximino-C1 -C4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, hetaryl, hetaryloxy, C3 -C6 -cycloalkyl, C1 -C4 -dialkylamino, CO2 Me, CO2 Et, formyl and acyl, Me being methyl, Et being ethyl and the expression hetaryl being an aromatic five-membered or sixmembered heterocyclic structure, with the exception of the following individual compounds of the general formula I where
A is CHOCH3, B is OCH3 and R is phenyl,
A is CHSCH3, B is OCH3 and R is phenyl,
A is CHCH3, B is OCH3 and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A is NOCH3, B is OCH3 and R is phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A is NOCH3, B is NHCH3 or R is CH3 or phenyl,
A is CHOCH3, B is NHCH3 and R is CH3 or phenyl and
A is CHSCH3, B is NHCH3 and R is phenyl, have excellent fungicidal, insecticidal, nematicidal and acaricidal activity.
The fungicidal and insecticidal activity is preferred.
The radicals stated for the general formula I may have, for example, the following meanings:
U, V and W may each be hydrogen, halogen (e.g. fluorine, chlorine, bromine or iodine), methyl or methoxy,
A may be C1 -C4 -alkylidene (e.g. methylidene, ethylidene, n-propylidene, isopropylidene, n-butylidene, isobutylidene, sec-butylidene or tert-butylidene), C1 -C4 -alkoxymethylidene t(e.g. methoxy-, ethoxy-, n-propoxy-, iso-propoxy-, n-butoxy-, isobutoxy-, sec-butoxy- or tert-butoxymethylidene), C1 -C4 -alkylthiomethylidene (e.g. methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, iso-butyl-, sec-butyl- or tert-butylthiomethylidene), C1 -C4 -alkoximino (e.g. methoximino, ethoximino, n-propoximino, isopropoximino, n-butoximino, isobutoximino, sec-butoximino or tert-butoximino),
B may be OH, C1 -C4 -alkoxy (e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy) or C1 -C4 -alkylamine (e.g. methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine or tert-butylamine), and
R is hydrogen, halogen (fluorine, chlorine, bromine or iodine), cyano, CF3 straight-chain or branched C1 -C10 -alkyl (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl or n-decyl), C3 -C6 -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), unsubstituted or substituted aryl (e.g. phenyl, naphthyl or anthryl), halo-C1 -C4 -alkyl (e.g. bromomethyl, chloromethyl, iodomethyl or CF3 -methyl), C2 -C6 -alkenyl (e.g. vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 3-methyl-2-butenyl or 2-methyl-2-penten-5-yl), C2 -C4 -alkynyl (e.g. ethynyl or 1-propynyl), unsubstituted or substituted heterocyclyl (e.g. oxiranyl, 1-aziridinyl, 1-azetidinyl, 1-pyrrolidinyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 1-piperidinyl, 1-morpholinyl, 1-piperazinyl, 1,3-dioxanyl, 3-tetrahydrothiopyranyl), unsubstituted or substituted hetaryl (e.g. pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 4-pyrimidinyl, 2-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 5-isoxazolyl, 3-isoxazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl, 2-benzothiazolyl), unsubstituted or substituted aryl-C2 -C4 -alkyl (e.g. benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-methyl-3-phenylpropyl, 2-methyl-2-phenylpropyl or 4-phenylbutyl), unsubstituted or substituted aryl-C1 -C4 -alkenyl (e.g. phenyl-1-ethenyl, 2-phenyl-1-propenyl, 2,2-diphenylethenyl, 1-phenyl-1-propen-2-yl or 1-phenyl-1-ethenyl), unsubstituted or substituted arylethynyl (e.g. phenylethynyl), unsubstituted or substituted hetaryl-C1 -C4 -alkyl (e.g. pyridylmethyl or 3-pyridylmethyl), C1 -C4 -alkoxy-C1 -C4 -alkyl (e.g. methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, 2-methoxyprop-2-yl, 2-ethoxyprop-2-yl, 2-n-propoxyprop-2-yl, isopropoxyprop-2-yl, 2-n-butoxyprop-2-yl, isobutoxyprop-2-yl, sec-butoxyprop-2-yl or tert-butoxyprop-2-yl), unsubstituted or substituted aryloxy-C1 -C4 -alkyl (e.g. phenoxymethyl), unsubstituted or substituted hetaryloxy-C1 -C4 -alkyl (e.g. 2-thienyloxymethyl), unsubstituted or substituted arylamino-C1 -C4 -alkyl (e.g. N-(phenylamino)-methyl), C(O)R1 (e.g. C(O)CH3, C(O)CH2 CH3 or C(O)phenyl), C(O)NR2 R3 (e.g. C(O)NH2, C(O)NHCH3), C(S)NR2 R3 (e.g. C(S)NH2 or C(S)NHCH3), C(O)SR6 (e.g. C(O)SCH3 or C(O)SCH2 C6 H5), C(O)OR7 (e.g. CO2 CH3 or CO2 CH2 C6 H5), C(S)SR8 (e.g. CS2 CH3), CH(OH)R9 (e.g. H(OH)C6 H5), CH(OR10)R11 (e.g. CH(OCH3)C6 H5), SiR12 R13 R14 (e.g. SiMe3 ) SnR15 R16 R17 (e.g. SnMe3), C(O)R18 (e.g. CO2 Me, CO2 CH2 C6 H5) or C(═N--OR19)R20 (e.g. C(NOMe)C6 H5).
R1 -R17, R19 and R20 are, for example, hydrogen C1 -C4 -alkyl (e.g. methyl, ethyl, n- and isopropyl, n-, iso-, sec- and tert-butyl), unsubstituted or substituted aryl (e.g. 2-chlorophenyl, 3,5-dimethylphenyl and 1-methyl-2-naphthyl), unsubstituted or substituted hetaryl (e.g. 6-chloro-2-pyrridyl, 4-pyrimidinyl, 2-furyl and 6-methyl-benzthiazol-2-yl), unsubstituted or substituted arylalkyl (e.g. 2-chlorobenzyl and 3,5-dichlorobenzyl) and unsubstituted or substituted hetarylalkyl (e.g. 2-furylmethyl and 6-methyl-2-pyridylmethyl) and R18 is, for example, OH, C1 -C4 -alkoxy (e.g. methoxy and ethoxy) and unsubstituted or substituted aryl-C1 -C4 -alkoxy (e.g. 2-chlorobenzyloxy).
The radicals defined above as unsubstituted or substituted contain as substituents, apart from hydrogen, for example fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, tert-butoxy, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methoximinomethyl, ethoximinomethyl, n-propoximinomethyl, n-butoximinomethyl, n-pentoximinomethyl, n-hexyloximinomethyl, allyloximinomethyl, benzyloximinomethyl, isopropoximinomethyl, isobutoximinomethyl, tert-butoximinomethyl, methylimino-1-ethyl, ethoximino-1-ethyl, n-propoximino-1-ethyl, n-butoximino-1-ethyl, n-pentoximino-1-ethyl, n-hexoximino-1-ethyl, allyloximino-1-ethyl, benzyloximino-1-ethyl, phenyl, phenoxy, benzyl, benzyloxy, imidazol-1-yl, piperazin-1-yl, 4-morpholinyl, piperidin-1-yl, pyridyl-2-oxy, cyclopropyl, cyclohexyl, oxiranyl, 1,3-dioxan-2-yl, 1,3-dioxan-2-yl, tetrahydropyran-2-yloxy, dimethylamino, diethylamino, CO2 Me, CO2 Et, formyl or acyl, Me being methyl and Et being ethyl.
The compounds of the general formula I ##STR3## where U, V and W are each hydrogen,
A is ethylidene, methoxymethylidene or methoximino,
B is methoxy or methylamine and
R has the abovementioned meanings, are preferred.
Owing to the C═C or C═N double bonds, the novel compounds of the general formula I may be obtained in the preparation as E/Z isomer mixtures. These can be separated into the individual components in a conventional manner, for example by crystallization or chromatography. Both the individual isomeric compounds and mixtures thereof form subjects of the invention and can be used as pesticides.
The compounds of the general formula I as claimed in claim 1 are prepared, for example, as described in the following schemes:
The novel compounds of the general formula I can be prepared by reacting, for example, an o-bromo compound 2 with a terminal acetylene derivative 3 in the presence of a transition metal catalyst, preferably a palladium compound, e.g. Pd(PPh3)4, PdCl2 or Pd(OAc)2, in the presence of triphenylphosphine and in the presence of a base, for example an N-alkylamine, such as triethylamine, and in the presence or absence of a solvent or diluent, e.g. dimethylformamide or acetonitrile (cf. for example L. Brandsma et al., Synth. Comm. 20 (1990), 1889 and W. B. Austin et al., J. Org. Chem. 46 (1981), 2280). ##STR4##
A, B, R, U, V and W have the meanings stated in claim 1.
Alternatively, the compounds of the general formula 1 are obtained by reacting the o-bromo-α-keto acid derivatives 4 with the acetylenes of the formula 3 (conditions similar to Scheme 1) ##STR5## and then reacting the resulting α-ketocarboxylic acid derivatives 5 a) for example in a Wittig or a Wittig-Horner-Emmons reaction with a phosphonium ylide 6 or with a phosphonic acid derivative 7 (Scheme 3) to give the novel compounds of the formula 1, where B, U, V, W and R have the meanings stated in claim 1 and A is CH-alkyl, CH-alkoxy or CH-thioalkyl (cf. for example C. Ferri, Reaktionen der organischen Synthese, Thieme Verlag, Stuttgart, page 354 et seq., 1978), or R'=CH3, M.sup.⊕ =alkali metal ion Scheme 3
b) with an O-alkylhydroxylamine 8, in the presence or absence of an acid, e.g. hydrochloric acid, or of a ##STR6## bse, e.g. K2 CO3, to give the novel compounds of the formula 1 in which B, U, V, W, R and R4 have the meanings stated in claim 1 (cf. for example European Patent 253,213). ##STR7##
The novel compounds of the general formula 1 can also be prepared by reacting the terminal acetylenes 9, by a transition metal (TM)-catalyzed coupling, with the halides 10, preferably with the bromides (X=Br), or the iodides (X=I) in the presence of a catalyst, e.g. PdCl2, Pd(OAc)2 or Pd(PPh3)4, and of a base, such as triethylamine (cf. for example P. C. Vollhardt, Angew. Chem. 98 (1986), 268 and H. Yamanaka, Synthesis (1983), 312). Scheme 5
A, B, R, U, V and W have the meanings stated in claim 1.
In an alternative procedure, the α-keto acid derivatives of the terminal acetylenes 11 can be converted with the halides 10 under transition metal ##STR8## (TM)-catalysis into the derivatives 5, and the latter can be converted as described above into the novel compounds of the formula 1. ##STR9##
In a further possible method for the preparation of the compounds of the general formula 1, the acetylene group in formula 12 is first produced by a known method (cf. for example Houben-Weyl, Vol. V/2a, page 33 et seq. (Viehe) or see Schemes 1+2) ##STR10## and the group Y is then converted into the group ##STR11##
Schemes 7-9 are intended to illustrate this. The ketocarboxylic esters 17 can be prepared starting from the o-bromobenzaldehydes 13. ##STR12##
The o-bromobenzaldehydes 12 can be reacted with the terminal acetylenes 3 under transition metal catalysis to give the aldehydes 14 (cf. W. B. Austin, J. Org. Chem. 46 (1981), 2280).
The cyanohydrins 15 are obtained from the aldehydes 14 by reaction with a metal cyanide, such as NaCN or KCN, in the presence of an acid, e.g. hydrochloric acid (cf. for example Organikum, 16th Edition, page 445 (1986)).
The mandelic acid derivatives 16 can be prepared from the cyanohydrins 15 via a Pinner reaction (cf., for example, Org. Synth. Coll. 4 (1963), 58).
Oxidation of the mandelic acid derivatives 16, for example with a chromium compound, such as chromium trioxide, with sodium hypochlorite or with TEMPO gives the α-ketoesters 17 (cf. for example Houben-Weyl, Vol. 4/lb, pages 425-464 (1975); TEMPO=tetramethylpiperidin-1-oxyl).
The novel compounds of the formula 1a, in which A, U, V, W and R have the meanings stated in claim 1 and B is CO2 Me, can be prepared from the ketoesters 17, as shown in Schemes 3 and 4. The α-ketocarboxylic esters 17 can be synthesized starting from the halogen derivatives 18, by Grignard reaction with oxalic acid compounds 19 similarly to Scheme 8 (cf., for example, J. S. Nimitz, J. Org. Chem. 46 (1981), 211). ##STR13##
In a further possible method, carboxylic acids 20 are converted via the stage of the acyl chlorides into the cyanides 21 and the latter are converted into the ketoesters 17 by a Pinner reaction. ##STR14## (cf. for example Organikum, 16th Edition, 423 et seq. (1986) and Angew. Chem. 94 (1982), 1).
The novel compounds of the formula 1 where A, X, Y, Z and R have the meanings stated in claim 1 and B is hydroxyl or alkylamino can be prepared from the carboxylic ester derivatives 1a. ##STR15##
The carboxylic acids 22 are obtained by hydrolysis by known methods (cf. Organikum, 16th Edition, page 415 et seq. and page 622 (1986)).
They can be converted into the acyl chlorides 23 (cf. Organikum, 16th Edition, page 423 et seq. (1986)).
The amides 24 are either obtained from these in a conventional manner (Organikum, 16th Edition, page 412 (1986)) or alternatively from the carboxylic esters 1a directly by aminolysis with amines.
However, the novel compounds of the general formula I can also be prepared by converting a suitably substituted styryl compound 25 in a conventional manner into the corresponding acetylene derivative 1. ##STR16##
Where X is H and Y is halogen or X is halogen and Y is H, the reaction is carried out in the presence of a base, e.g. sodium hydride, potassium hydroxide, Triton B or n-butyllithium (cf. for example H. Zimmer et al., Chimia 28 (1974), page 656 et seq.) (Triton B=2-benzyltrimethylammonium hydroxide).
Where X and Y are each halogen, the cleavage can be carried out with zinc (cf. for example H. G. Viehe, Chemistry of Acetylenes, Marcel Dekker, New York, 1969, page 134 et seq.).
The Examples which follow illustrate the preparation of the compounds.
Preparation of methyl 2-ethynylphenylglyoxylate O-methyloxime (compound 1, Table 2)
33.3 g (0.35 mol) of trimethylsilylacetylene, 3.8 g of palladium(II) acetate, 3.2 g of copper(I) iodide and 8.9 g of triphenylphosphine are added to a solution of 55.4 g (0.23 mol) of methyl 2-bromophenylglyoxylate in 415 ml of triethylamine, and nitrogen is then passed through the solution for 30 minutes. The reaction mixture is then heated at 90° C. for 45 minutes, is allowed to cool and is filtered off. The filtrate is evaporated down, the residue is taken up in ethyl acetate and the solution is washed with water. The organic phase is dried and evaporated down. 56.8 g of α-ketoester remain as a black oil.
The crude product prepared in this manner is dissolved in 50 ml of methanol, 38.9 g (0.37 mol) of O-methylhydroxylamine hydrochloride are added and heating is carried out for 15 minutes at 60° C. The mixture is evaporated down, the residue is taken up in ethyl acetate and the solution is washed with water. The organic phase is dried and evaporated down. 52.4 g of compound No. 2 (Table 2) remain as a black oil. 1 H-NMR (CDCl3 /TMS): δ=0.22 (s, 9H, SiMe3); 3.86; 4.06 (s, 3H, OCH3); 7.25-7.61 ppm (m, 4H, aryl).
The trimethylsilylacetylene compound prepared in this manner is dissolved in 320 ml of methanol and stirred together with 3.2 g of potassium carbonate for 1 hour at room temperature (20° C.). The mixture is then evaporated down, the residue is taken up in methylene chloride and the solution is washed with 10% strength sodium bicarbonate solution. The organic phase is dried and evaporated down. 36 g (72%, based on methyl 2-bromophenylglyoxylate) of compound 1 (Table 2) remain as a black solid. 1 H-NMR (CDCl3 /TMS): δ=3.17 (s, 3H, ═C--H); 3.87; 4.07 (s, 3H, OCH3); 7.27-7.60 ppm (m, 4H, aryl).
a) Preparation of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate O-methyloxime (European Patent 253,213, No. 136)
300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mg of copper(I) iodide and 11 g (0.095 mol) of 2-methylphenylacetylene are added to a solution of 10 g (0.041 mol) of methyl 2-bromophenylglyoxylate in 50 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 3 hours at 80° C. After cooling, methylene chloride is added and the solution is washed with water. The organic phase is dried and evaporated down. 16.5 g of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate remain as a black oil. 1 H-NMR (CDCl3 /TMS): δ=2.53 (s, 3H, CH3); 3.81 (s, 3H, OCH3); 7.13-7.88 ppm (m, 8H, aryl).
7.4 g (0.089 mol) of methoxyamine hydrochloride are added to the ketoester obtained in this manner, in 20 ml of methanol, and refluxing is carried out for 1.5 hours. The mixture is evaporated down, the residue is taken up in ethyl acetate, the solution is washed with water and the organic phase is dried and evaporated down. 9.5 g of the product remain as a black oil, which can be recrystallized from methanol. The abovementioned compound is obtained in this manner as a colorless solid having a melting point of 92°-96° C. 1 H-NMR (CDCl3 /TMS): δ=2.46 (s, 3H, CH3); 3.83; 4.07 (s, 3H, OCH3); 7.12-7.63 ppm (m, 8H, aryl).
b) N-Methyl-2-(2-methylphenylethynyl)-phenylglyoxylamide O-methyloxime (compound 32, Table 4)
2 g (7 mmol) of the compound prepared in Example 2a are added to 50 ml of a 40% strength methylamine solution and the mixture is stirred overnight at room temperature. Extraction with ether, drying and evaporation are then carried out. 0.9 g (42%) of compound 32 (Table 4) remains as a pale yellow solid of melting point 128°-129° C. 1 H-NMR (CDCl3 /TMS): δ=2.43 (s, 3H, CH3); 2.91 (d, 3H, NCH3); 3.96 (s, 3H, OCH3); 6.75 (br, 1H, NH); 7.14-7.63 ppm (m, 8H, aryl).
Methyl 2-(2-(3-chloro)thienylethynyl)-phenylglyoxylate O-methyloxime (compound 178, Table 2)
100 mg of palladium(II) acetate, 87 mg of copper(I) iodide and 240 mg of triphenylphosphine are added to a solution of 2 g (0.009 mol) of methyl 2-ethynylphenylglyoxylate O-methyl oxime (Example 1) and 3.6 g (0.018 mol) of 2-bromo-3-chlorothiophene in 100 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 1 hour at 90° C. The solid formed is filtered off and the filtrate is evaporated down. The residue is taken up in ethyl acetate, the solution is washed with water and the organic phase is dried and evaporated down.
The remaining crude product is chromatographed over silica gel using hexane/methyl tert-butyl ether.
As the first fraction, 700 mg (23%) of compound 178 (Table 2) are obtained in the form of a brown oil. 1 H-NMR (CDCl3 /TMS): δ=3.88; 4.09 (s, 3H, OCH3); 6.93 (d, 1H, ═CH); 7.25 (d, 1H, ═CH); 7.27-7.66 ppm (m, 4H, aryl).
500 mg (13%) of dimeric starting material are obtained as the second fraction (compound 162, Table 2). 1 H-NMR (CDCl3 /TMS): δ=3.91; 4.09 (s, 3H, OCH3); 7.27-7.61 ppm (m, 4H, aryl).
2. Method 1: Methyl α-[2-(phenylethynyl)-phenyl]-β-methylacrylate [European Patent 280,185, No. 136]
300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mg of copper(I) iodide are added to a solution of 10 g (0.041 mol) of methyl 2-bromophenylglyoxylate and 6.3 g (0.061 mol) of phenylacetylene in 50 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 90 minutes at 90° C. It is then evaporated down and the residue is taken up in methylene chloride. The solution is washed with water, dried and evaporated down. The remaining residue is chromatographed over silica gel using hexane/methyl tert-butyl ether. 5.5 g of α-ketoester remain as a brown oil after evaporating down. 1 H-NMR (CDCl3 /TMS): δ=2.82 (s, 3H, CH3); 7.36-7.88 ppm (m, 9H, aryl).
2.4 g (0.021 mol) of potassium tert-butylate are added at 5° C. to a solution of 8.7 g (0.021 mol) of ethyltriphenylphosphonium iodide in 60 ml of dry tetrahydrofuran. Stirring is carried out for 1 hour at this temperature, after which a solution of 5.5 g (0.021 mol) of α-ketoester (see above) in 20 ml of tetrahydrofuran is added dropwise at 5° C. and stirring is continued for 3 hours at room temperature. The reaction batch is poured onto water and extracted with methylene chloride, and the organic phase is dried and evaporated down. Chromatography over silica gel using hexane/methyl tert-butyl ether gives 1.2 g of the compound [European Patent 280,185, No. 136] as a brown oil in the form of an E/Z mixture. 1 H-NMR (CDCl3 /TMS): δ=1.74 (d, 3H, CH3 -isomer A); 2.22 (d, 3H, CH3 -isomer B); 3.70; 3.71 (s, 3H, CH3 -isomer A, B); 6.38 (q, 1H, CH); 7.17-7.61 ppm (m, 9H, aryl).
Preparation of methyl α-{2-[2-(4-chlorophenyl)-isoxazol-5-ylethynyl]-phenyl}-β-methoxyacrylate (compound 195, Table 1)
0.8 g of methyl α-{2-[2-chloro-2-(3-[4-chlorophenyl]-isoxazol-5-yl)-ethenyl]-phenyl}-β-methoxyacrylate (European Patent 378,755) is dissolved in 10 ml of anhydrous dimethyl sulfoxide, and a pinch of sodium hydride is added. Stirring is carried out overnight at room temperature, and the mixture is poured onto ice water and extracted three times with dichloromethane. The combined organic phases are washed three times with water, dried over sodium sulfate and then evaporated down in a rotary evaporator. The residue is triturated with diisopropyl ether. 0.3 g of the title compound is obtained as colorless crystals of melting point 107°-110° C. 1 H-NMR (CDCl3 /TMS), δ=3.7 (s, 3H); 3.85 (s, 3H); 6.7 (s, 1H); 7.2-7.8 (m, 9H).
Preparation of 2-ethynylphenylglyoxylic acid-N-methylamide-O-methyloxime
1 g (4.6 mmol) of the acetylene compound prepared in Example 1 is added to 20 ml of a 40% strength methylamine solution, and the mixture is stirred for 45 minutes at 40°-50° C. The solution is extracted with methyl tert-butyl ether, dried and evaporated down. 700 mg (70%) of the compound remain as a colorless solid.
1 H-NMR (CDCl3 /TMS): δ=2.99 (d, 2H, NCH3); 3.13 (s, 1H, .tbd.C--H), 3.98 (s, 3H, OCH3), 6.80 (br, 1H, NH); 7.21-7.58 ppm (m, 4H).
Preparation of methyl 2-benzoyl-ethynylphenylglyoxylate O-methyloxime (compound 26, Table 6)
Under a nitrogen blanket and at 90° C., 2 g (9.2 mmol) of the acetylene derivative from Example 1 is added to a mixture of 50 mg of copper(II) chloride, 110 mg of palladium(II) acetate, 380 mg of triphenylphosphine and 2.6 g (18.4 mmol) of benzoyl chloride in 100 ml of triethylamine. After 30 minutes, the mixture is allowed to cool and the solid is filtered off. The filtrate is evaporaed down, and the residue is taken up in methyl tert-butyl ether, washed with water, dried and evaporated down. The residue is stirred with diethyl ether and the precipitated pale brown solid is filtered off. 2.0 g (68%) of compound 26, Table 6, remain. Mp. 89°-94° C.
Preparation of methyl 2-(methoxyiminobenzoyl)ethynylphenylglyoxylate O-methyloxime (compound 10, Table 9).
A mixture of 1.5 g (4.7 mmol) of compound 26 from Table 6 (from Example 6) and 2.6 g of O-methylhydroxylamine hydrochloride in 5 ml of methanol is heated for 90 min at 60° C. The mixture is evaporated down and the residue is taken up in methyl tert-butyl ether and washed with water, followed by drying and evaporating down. The residue is chromatographed on silica gel using mixtures of methyl tert-butyl ether and hexane. 1.1 g (67%) of compound 10 from Table 9 remain as a yellow oil (isomer mixture).
1 H-NMR (CDCl3 /TMS): δ=3.81; 4.04; 4.12 (3H, OCH3); 7.28-7.88 ppm (9H).
TABLE 1
______________________________________
##STR17##
phys. data
(m.p. [°C.]);
IR [cm.sup.-1 ];
No. R .sup.1 H-NMR [δ scale]
______________________________________
1 H
2 SiMe.sub.3
3 S.sub.n Me.sub.3
4 I
5 CN
6 CH.sub.3
7 CH.sub.2 CH.sub.3
8 n-C.sub.3 H.sub.7
9 i-C.sub.3 H.sub.7
10 n-C.sub.4 H.sub.9
11 i-C.sub.4 H.sub.9
12 s-C.sub.4 H.sub.9
13 t-C.sub.4 H.sub.9
14 n-C.sub.5 H.sub.11
15 n-C.sub.6 H.sub.13
16 n-C.sub.7 H.sub.15
17 n-C.sub.8 H.sub.17
18 n-C.sub.9 H.sub.19
19 n-C.sub.10 H.sub.21
20 cyclopropyl
21 1-methyl-cycloprop-1-yl
22 cyclobutyl
23 cyclopentyl
24 cyclohexyl
25 cyclohex-1-en-1-yl
26 methoxymethyl
27 ethoxymethyl
28 phenoxymethyl
29 benzyloxymethyl
30 phenylmethyl
31 morpholino-N-methyl
32 phenylthiomethyl
33 2-methylphenyl
34 3-methylphenyl
35 4-methylphenyl
36 2-chlorophenyl
37 3-chlorophenyl
38 4-chlorophenyl
39 2-bromophenyl
40 3-bromophenyl
41 4-bromophenyl
42 2-fluorophenyl
43 3-fluorophenyl
44 4-fluorophenyl
45 2-iodophenyl
46 3-iodophenyl
47 4-iodophenyl
48 2-methoxyphenyl
49 3-methoxyphenyl
50 4-methoxyphenyl
51 2-ethoxyphenyl
52 3-ethoxyphenyl
53 4-ethoxyphenyl
54 2-n-propoxyphenyl
55 3-n-propoxyphenyl
56 4-n-propoxyphenyl
57 2-i-propoxyphenyl
58 3-i-propoxyphenyl
59 4-i-propoxyphenyl
60 2-n-butoxyphenyl
61 3-n-butoxyphenyl
62 4-n-butoxyphenyl
63 2-sec.-butoxyphenyl
64 3-sec.-butoxyphenyl
65 4-sec.-butoxyphenyl
66 2-iso-butoxyphenyl
67 3-isobutoxyphenyl
68 4-isobutoxyphenyl
69 2-tert.-butoxyphenyl
70 3-tert.-butoxyphenyl
71 4-tert.-butoxyphenyl
72 2-ethylphenyl
73 3-ethylphenyl
74 4-ethylphenyl
75 2-n-propylphenyl
76 3-n-propylphenyl
77 4-n-propylphenyl
78 2-i-propylphenyl
79 3-i-propylphenyl
80 4-i-propylphenyl
81 2-n-butylphenyl
82 3-n-butylphenyl
83 4-n-butylphenyl
84 2-isobutylphenyl
85 3-isobutylphenyl
86 4-isobutylphenyl
87 2-sec.-butylphenyl
88 3-sec.-butylphenyl
89 4-sec.-butylphenyl
90 2-tert.-butylphenyl
91 3-tert.-butylphenyl
92 4-tert.-butylphenyl
93 2-NO.sub.2 -phenyl
94 3-NO.sub.2 -phenyl
95 4-NO.sub.2 -phenyl
96 2-CF.sub.3 -phenyl
97 3-CF.sub.3 -phenyl
98 4-CF.sub.3 -phenyl
99 2-CN-phenyl
100 3-CN-phenyl
101 4-CN-phenyl
102 2-(CH.sub.2 CN)-phenyl
103 3-(CH.sub.2 CN)-phenyl
104 4-(CH.sub.2 CN)-phenyl
105 2-CH.sub.3 CO-phenyl
106 3-CH.sub.3 CO-phenyl
107 4-CH.sub. 3 CO-phenyl
108 2-CHO-phenyl
109 3-CHO-phenyl
110 4-CHO-phenyl
111 2-NMe.sub.2 -phenyl
112 3-NMe.sub.2 -phenyl
113 4-NMe.sub.2 -phenyl
114 2-CO.sub.2 Me-phenyl
115 3-CO.sub.2 Me-phenyl
116 4-CO.sub.2 Me-phenyl
117 2-CO.sub.2 Et-phenyl
118 3-CO.sub.2 Et-phenyl
119 4-CO.sub.2 Et-phenyl
120 2-OCF.sub.3 -phenyl
121 3-OCF.sub.3 -phenyl
122 4-OCF.sub.3 -phenyl
123 2-phenyl-phenyl
124 3-phenyl-phenyl
125 4-phenyl-phenyl
126 2-phenoxy-phenyl
127 3-phenoxy-phenyl
128 4-phenoxy-phenyl
129 3,4-OCH.sub.2 O-phenyl
130 3,4-OCH.sub.2 CH.sub.2 -phenyl
131 3,4,5-(OCH.sub.3).sub.3 -phenyl
132 3,4-(OCH.sub.3).sub.2 -phenyl
133 2,3-Me.sub.2 -phenyl
134 2,4-Me.sub.2 -phenyl
135 2,5-Me.sub.2 -phenyl
136 2,6-Me.sub.2 -phenyl
137 3,4-Me.sub.2 -phenyl
138 3,5-Me.sub.2 -phenyl
139 2,4,6-Me.sub.3 -phenyl
140 2,3-Cl.sub.2 -phenyl
141 2,4-Cl.sub.2 -phenyl
142 2,5-Cl.sub.2 -phenyl
143 2,6-Cl.sub.2 -phenyl
144 3,4-Cl.sub.2 -phenyl
145 3,5-Cl.sub.2 -phenyl
146 2-methyl, 5-NO.sub.2 -phenyl
147 2-methyl, 3-NO.sub.2 -phenyl
148 2-methyl, 4-F-phenyl
149 4-methyl, 3-F-phenyl
150 2,6-Cl.sub.2, 4-NO.sub.2 -phenyl
151 2-NO.sub.2, 4-Cl-phenyl
152 2-Cl, 5-CF.sub.3 -phenyl
153 4-Cl, 3-CF.sub.3 -phenyl
154 2-methyl, 4-CH.sub.3 CO-phenyl
155 2-methyl, 5-CH.sub.3 CO-phenyl
156 2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl
157 2-Me, 4-methoximinomethyl-phenyl
158 2-Me, 5-methoximinomethyl-phenyl
159 2,5-Me.sub.2, 4-methoximinomethyl-phenyl
160 2-Me, 4-ethoximinomethyl-phenyl
161 2-Me, 4-n-propoximinomethyl-phenyl
162 2-Me, 4-i-propoximinomethyl-phenyl
163 2-Me, 4-n-butoximinomethyl-phenyl
164 2-Me, 5-ethoximinomethyl-phenyl
165 2,5-Me.sub.2, 4-ethoximinomethylphenyl
166 3-(5-phenyl-1,3,4-oxadiazol-2-yl)-
phenyl
167 3-(5-naphthyl-1,3,4-oxa-
diazol-2-yl)-phenyl
168 2-pyridyl
169 3-pyridyl
170 4-pyridyl
171 5-methyl-2-pyridyl
172 6-methyl-2-pyridyl
173 quinolin-3-yl
174 2,8(CF.sub.3).sub.2 -quinolin-4-yl
175 Isoquinolin-4-yl
176 thien-2-yl
177 thien-3-yl
178 2-chloro-thien-3-yl
179 2-chloro-thien-4-yl
180 3-chloro-thien-2-yl
181 2-chloro-thien-5-yl
182 2,5-Cl.sub.2 -thien-3-yl
183 3-furyl
184 2-(isoxazol-3-yl)-thien-5-yl
185 2-cyano-thien-3-yl
186 3-Me-thien-2-yl
187 2-NO.sub.2 -thien-5-yl
188 3-benzothienyl
189 3,5-Me.sub.2 -isoxazol-3-yl
190 2-thiazolyl
191 5-NO.sub.2 -thiazol-2-yl
192 5-NO.sub.2 -imidazol-4-yl
193 4-pyrrazolyl
194 3,5-Me.sub.2 -pyrrazol-4-yl
195 3-(4-Cl-phenyl)-isoxazol-5-yl
107-110° C.
196 4-chloro-3-(3-chlorophenyl)-
isoxazol-5-yl
197 5-(4-methylphenyl)-1,3,4-
oxadiazol-2-yl
198 5-phenyl-1,3,4-thiadiazol-2-yl
199 3-(4-chlorophenyl)-1,2,4-
oxadiazol-5-yl
200 3-isopropyl-isoxazol-5-yl
201 5-(4-F-phenyl)-isoxazol-3-yl
202 4-ethyl-5-phenyl-isoxazol-3-yl
203 4-chloro-5-(3-Cl-phenyl)-
isoxazol-3-yl
204 CH.sub.2 Br
205 CH.sub.2 Cl
206 CH.sub.2 I
207 1-naphthyl
208 2-naphthyl
209 6-methoxy-napht-2-yl
______________________________________
TABLE 2
______________________________________
##STR18##
phys. data
(m.p. [°C.]);
IR [cm.sup.-1 ];
No. R .sup.1 H-NMR [δ scale]
______________________________________
1 H 3.17 (CH); 3.87;
4.07 (Me);
7.27-7.60
(aryl)
2 SiMe.sub.3 0.22;
3.86; 4.06 (Me);
7.25-7.61
(aryl)
3 SnMe.sub.3
4 I
5 CN
6 CH.sub.3
7 CH.sub.2 CH.sub.3
8 n-C.sub.3 H.sub.7
9 i-C.sub.3 H.sub.7
10 n-C.sub.4 H.sub.9
11 i-C.sub.4 H.sub.9
12 s-C.sub.4 H.sub.9
13 t-C.sub.4 H.sub.9
14 n-C.sub.5 H.sub.11
15 n-C.sub.6 H.sub.13
16 n-C.sub.7 H.sub.15
17 n-C.sub.8 H.sub.17
18 n-C.sub.9 H.sub.19
19 n-C.sub.10 H.sub.21
20 cyclopropyl
21 1-methyl-cycloprop-1-yl
22 cyclobutyl
23 cyclopentyl
24 cyclohexyl 1.23-2.61
(cyclohexyl);
3.85; 4.05 (Me);
7.22-7.48
(aryl)
25 cyclohex-1-en-1-yl 98-100° C.
26 methoxymethyl 3.41; 3.87; 4.07
(Me); 4.28
(CH.sub.2); 7.28-
7.55 (aryl)
27 ethoxymethyl
28 phenoxymethyl
29 benzyloxymethyl
30 phenylmethyl
31 morpholino-N-methyl 2.59; 3.49; 3.76
(CH.sub.2); 3.87;
4.07 (Me); 7.23-
7.71 (aryl)
32 phenylthiomethyl
33 3-methyl-phenyl 95-99° C.
34 3-chloro-phenyl 3.86; 4.09 (Me);
7.25-7.63
(aryl)
35 4-chloro-phenyl 91-96° C.
36 3-bromo-phenyl
37 3-fluorophenyl
38 4-fluorophenyl
39 2-iodo-phenyl
40 3-iodo-phenyl
41 4-iodo-phenyl
42 3-methoxy-phenyl 3.82; 3.84; 4.08
(Me); 6.87-7.63
(aryl)
43 4-methoxy-phenyl 118-121° C.
44 2-ethoxy-phenyl
45 3-ethoxy-phenyl
46 4-ethoxy-phenyl 1.42; 3.84; 4.07
(Me); 4.05
(CH.sub.2); 6.84-
7.61 (aryl)
47 2-n-propoxy-phenyl
48 3-n-propoxy-phenyl
49 4-n-propoxy-phenyl
50 2-i-propoxy-phenyl
51 3-i-propoxy-phenyl 1.34; 3.87; 4.08
(Me); 4.57
(CH); 6.75-
7.61 (aryl)
52 4-i-propoxy-phenyl
53 2-n-butoxy-phenyl
54 3-n-butoxy-phenyl
55 4-n-butoxy-phenyl
56 2-sec.-butoxy-phenyl
57 3-sec.-butoxy-phenyl
58 4-sec.-butoxy-phenyl
59 2-iso-butoxy-phenyl
60 3-iso-butoxy-phenyl
61 4-iso-butoxy-phenyl
62 2-tert.-butoxyphenyl
63 3-tert.-butoxyphenyl
64 4-tert.-butoxyphenyl
65 2-ethyl-phenyl
66 3-ethyl-phenyl
67 4-ethyl-phenyl 1.23; 3.84; 4.09
(Me); 2.65
(CH.sub.2); 7.17-
7.63 (aryl)
68 2-n-propyl-phenyl
69 3-n-propyl-phenyl
70 4-n-propyl-phenyl
71 2-i-propyl-phenyl
72 3-i-propyl-phenyl
73 4-i-propyl-phenyl 1.24; 3.85; 4.09
(Me); 2.91
(CH); 7.20-
7.61 (aryl)
74 2-n-butylphenyl
75 3-n-butylphenyl
76 4-n-butylphenyl
77 2-iso-butyl-phenyl
78 3-iso-butyl-phenyl
79 4-iso-butyl-phenyl
80 2-sec.-butylphenyl
81 3-sec.-butylphenyl
82 4-sec.-butylphenyl
83 2-tert.-butylphenyl
84 3-tert.-butylphenyl
85 4-tert.-butylphenyl 1.31; 3.85; 4.09
(Me); 7.35-
7.61 (aryl)
86 3-NO.sub.2 -phenyl 122-125° C.
87 4-NO.sub.2 -phenyl 160-164° C.
88 2-CF.sub.3 -phenyl 66-70° C.
89 3-CF.sub.3 -phenyl 3.86; 4.09 (Me);
7.33-7.73
(aryl)
90 2-CN-phenyl
91 3-CN-phenyl
92 4-CN-phenyl 145-149° C.
93 2-(CH.sub.2 CN)-phenyl 3.82; 4.04 (Me);
3.92 (CH.sub.2);
7.25-7.65
(aryl)
94 3-(CH.sub.2 CN)-phenyl 3.75 (CH.sub.2);
3.84; 4.08 (Me);
7.33-7.63 (aryl)
95 4-(CH.sub.2 CN)-phenyl 85-90° C.
96 2-CH.sub.3 CO-phenyl
97 3-CH.sub.3 CO-phenyl
98 4-CH.sub.3 CO-phenyl 121-123° C.
99 2-CHO-phenyl
100 3-CHO-phenyl 3.87; 4.10 (Me);
7.36-7.94;
(aryl; 10.01
(CH)
101 4-CHO-phenyl 104-106° C.
102 2-NMe.sub.2 -phenyl
103 3-NMe.sub.2 -phenyl
104 4-NMe.sub.2 -phenyl 2.99; 3.82; 4.06
(Me);
6.59-7.55
(aryl)
105 2-CO.sub.2 Me-phenyl
106 3-CO.sub.2 Me-phenyl 3.86; 3.94; 4.09
(Me);
7.35-8.14
(aryl)
107 4-CO.sub.2 Me-phenyl
108 2-CO.sub.2 Et-phenyl
109 3-CO.sub.2 Et-phenyl
110 4-CO.sub.2 Et-phenyl
111 2-OCF.sub.3 -phenyl
112 3-OCF.sub.3 -phenyl
113 4-OCF.sub.3 -phenyl
114 2-phenyl-phenyl 3.79; 4.01 (Me);
7.23-7.61
(aryl)
115 3-phenyl-phenyl 3.85; 4.09 (Me);
7.38-7.73 (aryl)
116 4-phenyl-phenyl 137-142° C.
117 2-phenoxy-phenyl
118 3-phenoxy-phenyl
119 4-phenoxy-phenyl 3.82; 4.07 (Me);
6.92-7.58
(aryl)
120 3,4-OCH.sub.2 O-phenyl 3.84; 4.07 (Me);
5.98 (CH.sub.2);
6.76-7.58
(aryl)
121 3,4-OCH.sub.2 CH.sub.2 O-phenyl
3.84; 4.07 (Me);
4.25 (CH.sub.2);
6.79-7.58
(aryl)
122 3,4,5-(OCH.sub.3).sub.3 -phenyl
3.86; 3.88;
3.89; 3.92;
4.10 (Me);
6.75-7.61
(aryl)
123 3,4-(OCH.sub.3).sub.2 -phenyl
124 2,3-Me.sub.2 -phenyl 105-109° C.
125 2,4-Me.sub.2 -phenyl 104-109° C.
126 2,5-Me.sub.2 -phenyl 142-147° C.
127 2,6-Me.sub.2 -phenyl
128 3,4-Me.sub.2 -phenyl 86-89° C.
129 3,5-Me.sub.2 -phenyl 2.30 (2x); 3.84;
4.08 (Me);
6.97-7.61 (aryl)
130 2,4,6-Me.sub.3 -phenyl 108-112° C.
131 2,3-Cl.sub.2 -phenyl 117-121° C.
132 2,4-Cl.sub.2 -phenyl 113-116° C.
133 2,5-Cl.sub.2 -phenyl 107-110° C.
134 2,6-Cl.sub.2 -phenyl 145-148° C.
135 3,4-Cl.sub.2 -phenyl 93-96° C.
136 3,5-Cl.sub.2 -phenyl 106-109° C.
137 2-methyl, 5-NO.sub.2 -phenyl
138 2-methyl, 3-NO.sub.2 -phenyl
139 2-methyl, 4-F-phenyl
140 4-methyl, 3-F-phenyl
141 2,6-Cl.sub.2, 4-NO.sub.2 -phenyl
142 2-NO.sub.2, 4-Cl-phenyl
143 2-Cl, 5-CF.sub.3 -phenyl
3.87; 4.07 (Me);
7.35-8.37 (aryl)
144 4-Cl, 3-CF.sub.3 -phenyl
145 2-methyl, 4-CH.sub.3 CO-phenyl
146 2-methyl, 5-CH.sub.3 CO-phenyl
147 2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl
148 2-Me, 4-methoximinomethyl-phenyl
2.22; 2.46;
3.86; 4.01;
4.09 (Me);
7.20-7.75
(aryl)
149 2-Me, 5-methoximinomethyl-phenyl
2.22; 2.45;
3.84; 3.99; 4.06
(Me); 7.17-7.71
(aryl)
150 2,5-Me.sub.2, 4-methoximinomethyl-phenyl
151 2-Me, 4-ethoximinomethyl-phenyl
152 2-Me, 4-n-propoximinomethyl-phenyl
153 2-Me, 4-i-propoximinomethyl-phenyl
154 2-Me, 4-n-butoximinomethyl-phenyl
155 2-Me, 5-ethoximinomethyl-phenyl
156 2,5-Me.sub.2, 4-ethoximinomethyl-phenyl
157 1-Me-2-naphthyl
158 1-naphthyl 3.82; 4.09 (Me);
7.35-8.37 (aryl)
159 2-naphthyl 114-118° C.
160 6-methoxy-2-naphthyl 3.86; 3.95; 4.11
(Me); 7.12-
7.94 (aryl)
161
##STR19## 2240 (CC, RA-MAN)
162
##STR20## 1725; 1441; 1258; 1209; 1069; 1037; 1013;
950
##STR21##
163
##STR22## 1727; 1437; 1324; 1309; 1264; 1215; 1069;
1040
##STR23##
164 3-(5-phenyl-1,3,4-oxadiazol-2-yl)-
44-52° C.
phenyl
165 3-(5-naphthyl-1,3,4-oxa-
diazol-2-yl)-phenyl
166 2-pyridyl 3.87; 4.09 (Me);
7.22-8.62
(8H)
167 3-pyridyl 78-82° C.
168 4-pyridyl
169 5-methyl-2-pyridyl
170 6-methyl-2-pyridyl
171 quinolin-3-yl
172 2,8(CF.sub.3).sub.2 -quinolin-4-yl
173 isoquinolin-4-yl
174 thien-2-yl 3.87; 4.09 (Me);
6.95-7.58
(aryl)
175 thien-3-yl 80-89° C.
176 2-chloro-thien-3-yl
177 2-chloro-thien-4-yl 3.84; 4.07 (Me);
6.98-7.58
(aryl)
178 3-chloro-thien-2-yl 3.88; 4.09 (Me);
6.93-7.66
(aryl)
179 2-chloro-thien-5-yl 3.87; 4.08 (Me);
6.81-7.59
(aryl)
180 2,5-Cl.sub.2 -thien-3-yl
181 3-furyl
182 2-(isoxazol-3-yl)-thien-5-yl
183 2-cyano-thien-3-yl
184 3-Me-thien-2-yl
185 2-NO.sub.2 -thien-5-yl
186 3-benzothienyl
187 3,5-Me.sub.2 -isoxazol-3-yl
188 2-thiazolyl
189 5-NO.sub.2 -thiazol-2-yl
190 5-NO.sub.2 -imidazol-4-yl
191 4-pyrrazolyl
192 3,5-Me.sub.2 -pyrrazol-4-yl
193 3-(4-Cl-phenyl)-isoxazol-5-yl
194 4-chloro-3-(3-chlorophenyl)-
isoxazol-5-yl
195 5-(4-methylphenyl)-1,3,4-
oxadiazol-2-yl
196 5-phenyl-1,3,4-thiadiazol-2-yl
197 3-(4-chlorophenyl)-1,2,4-
oxadiazol-5-yl
198 3-isopropyl-isoxazol-5-yl
199 5-(4-F-phenyl)-isoxazol-3-yl
200 4-ethyl-5-phenyl-isoxazol-3-yl
201 4-chloro-5-(3-Cl-phenyl)-iso-
oxalzol-3-yl
202 CH.sub.2 Br
203 CH.sub.2 Cl
204 CH.sub.2 I
205 9-anthracenyl 159-164° C.
206 2-methoxy-naphth-1-yl 129-137° C.
207 CHCH-phenyl 97-102° C.
208 4-(benzthiazol-2-yl)-phenyl
164-168° C.
209 1-pyrenyl 179-183° C.
______________________________________
TABLE 3
______________________________________
##STR24##
phys. data
(m.p. [°C.]);
IR [cm.sup.-1 ];
No. R .sup.1 H-NMR [δ scale]
______________________________________
1 H
2 SiMe.sub.3
3 SnMe.sub.3
4 I
5 CN
6 CH.sub.3
7 CH.sub.2 CH.sub.3
8 n-C.sub.3 H.sub.7
9 i-C.sub.3 H.sub.7
10 n-C.sub.4 H.sub.9
11 i-C.sub.4 H.sub.9
12 s-C.sub.4 H.sub.9
13 t-C.sub.4 H.sub.9
14 n-C.sub.5 H.sub.11
15 n-C.sub.6 H.sub.13
16 n-C.sub.7 H.sub.15
17 n-C.sub.8 H.sub.17
18 n-C.sub.9 H.sub.19
19 n-C.sub.10 H.sub.21
20 cyclopropyl
21 1-methyl-cycloprop-1-yl
22 cyclobutyl
23 cyclopentyl
24 cyclohexyl
25 cyclohex-1-en-1-yl
26 methoxymethyl
27 ethoxymethyl
28 phenoxymethyl
29 benzyloxymethyl
30 phenylmethyl
31 morpholino-N-methyl
32 phenylthiomethyl
33 3-methyl-phenyl
34 3-chloro-phenyl
35 4-chloro-phenyl
36 3-bromo-phenyl
37 3-fluorophenyl
38 4-fluorophenyl
39 2-iodo-phenyl
40 3-iodo-phenyl
41 4-iodo-phenyl
42 3-methoxy-phenyl
43 4-methoxy-phenyl
44 2-ethoxy-phenyl
45 3-ethoxy-phenyl
46 4-ethoxy-phenyl
47 2-n-propoxy-phenyl
48 3-n-propoxy-phenyl
49 4-n-propoxy-phenyl
50 2-i-propoxy-phenyl
51 3-i-propoxy-phenyl
52 4-i-propoxy-phenyl
53 2-n-butoxy-phenyl
54 3-n-butoxy-phenyl
55 4-n-butoxy-phenyl
56 2-sec.-butoxy-phenyl
57 3-sec.-butoxy-phenyl
58 4-sec.-butoxy-phenyl
59 2-iso-butoxy-phenyl
60 3-iso-butoxy-phenyl
61 4-iso-butoxy-phenyl
62 2-tert.-butoxyphenyl
63 3-tert.-butoxyphenyl
64 4-tert.-butoxyphenyl
65 2-ethyl-phenyl
66 3-ethyl-phenyl
67 4-ethyl-phenyl
68 2-n-propyl-phenyl
69 3-n-propyl-phenyl
70 4-n-propyl-phenyl
71 2-i-propyl-phenyl
72 3-i-propyl-phenyl
73 4-i-propyl-phenyl
74 2-n-butylphenyl
75 3-n-butylphenyl
76 4-n-butylphenyl
77 2-iso-butyl-phenyl
78 3-iso-butyl-phenyl
79 4-iso-butyl-phenyl
80 2-sec.-butylphenyl
81 3-sec.-butylphenyl
82 4-sec.-butylphenyl
83 2-tert.-butylphenyl
84 3-tert.-butylphenyl
85 4-tert.-butylphenyl
86 3-NO.sub.2 -phenyl
87 4-NO.sub.2 -phenyl
88 2-CF.sub.3 -phenyl
89 3-CF.sub.3 -phenyl
90 2-CN-phenyl
91 3-CN-phenyl
92 4-CN-phenyl
93 2-(CH.sub.2 CN)-phenyl
94 3-(CH.sub.2 CN)-phenyl
95 4-(CH.sub.2 CN)-phenyl
96 2-CH.sub.3 CO-phenyl
97 3-CH.sub.3 CO-phenyl
98 4-CH.sub.3 CO-phenyl
99 2-CHO-phenyl
100 3-CHO-phenyl
101 4-CHO-phenyl
102 2-NMe.sub.2 -phenyl
103 3-NMe.sub.2 -phenyl
104 4-NMe.sub.2 -phenyl
105 2-CO.sub.2 Me-phenyl
106 3-CO.sub.2 Me-phenyl
107 4-CO.sub.2 Me-phenyl
108 2-CO.sub.2 Et-phenyl
109 3-CO.sub.2 Et-phenyl
110 4-CO.sub.2 Et-phenyl
111 2-OCF.sub.3 -phenyl
112 3-OCF.sub.3 -phenyl
113 4-OCF.sub.3 -phenyl
114 2-phenyl-phenyl
115 3-phenyl-phenyl
116 4-phenyl-phenyl
117 2-phenoxy-phenyl
118 3-phenoxy-phenyl
119 4-phenoxy-phenyl
120 3,4-OCH.sub.2 O-phenyl
121 3,4-OCH.sub.2 CH.sub.2 -phenyl
122 3,4,5-(OCH.sub.3).sub.3 -phenyl
123 3,4-(OCH.sub.3).sub.2 -phenyl
124 2,3-Me.sub.2 -phenyl
125 2,4-Me.sub.2 -phenyl
126 2,5-Me.sub.2 -phenyl
127 2,6-Me.sub.2 -phenyl
128 3,4-Me.sub.2 -phenyl
129 3,5-Me.sub.2 -phenyl
130 2,4,6-Me.sub.3 -phenyl
131 2,3-Cl.sub.2 -phenyl
132 2,4-Cl.sub.2 -phenyl
133 2,5-Cl.sub.2 -phenyl
134 2,6-Cl.sub.2 -phenyl
135 3,4-Cl.sub.2 -phenyl
136 3,5-Cl.sub.2 -phenyl
137 2-methyl, 5-NO.sub.2 -phenyl
138 2-methyl, 3-NO.sub.2 -phenyl
139 2-methyl, 4-F-phenyl
140 4-methyl, 3-F-phenyl
141 2,6-Cl.sub.2, 4-NO.sub.2 -phenyl
142 2-NO.sub.2, 4-Cl-phenyl
143 2-Cl, 5-CF.sub.3 -phenyl
144 4-Cl, 3-CF.sub.3 -phenyl
145 2-methyl, 4-CH.sub.3 CO-phenyl
146 2-methyl, 5-CH.sub.3 CO-phenyl
147 2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl
148 2-Me, 4-methoximinomethyl-phenyl
149 2-Me, 5-methoximinomethyl-phenyl
150 2,5-Me.sub.2, 4-methoximinomethyl-phenyl
151 2-Me, 4-ethoximinomethyl-phenyl
152 2-Me, 4-n-propoximinomethyl-phenyl
153 2-Me, 4-i-propoximinomethyl-phenyl
154 2-Me, 4-n-butoximinomethyl-phenyl
155 2-Me, 5-ethoximinomethyl-phenyl
156 2,5-Me.sub.2, 4-ethoximinomethyl-phenyl
157 1-Me-2-naphthyl
158 1-naphthyl
159 2-naphthyl
160 6-methoxy-2-naphthyl
161 3-(5-phenyl-1,3,4-oxadiazol-2-yl)-
phenyl
162 3-(5-naphthyl-1,3,4-oxa-
diazol-2-yl)-phenyl
163 2-pyridyl
164 3-pyridyl
165 4-pyridyl
166 5-methyl-2-pyridyl
167 6-methyl-2-pyridyl
168 quinolin-3-yl
169 2,8(CF.sub.3).sub.2 -quinolin-4-yl
170 isoquinolin-4-yl
171 thien-2-yl
172 thien-3-yl
173 2-chloro-thien-3-yl
174 2-chloro-thien-4-yl
175 3-chloro-thien-2-yl
176 2-chloro-thien-5-yl
177 2,5-Cl.sub.2 -thien-3-yl
178 3-furyl
179 2-(isoxazol-3-yl)-thien-5-yl
180 2-cyano-thien-3-yl
181 3-Me-thien-2-yl
182 2-NO.sub.2 -thien-5-yl
183 3-benzothienyl
184 3,5-Me.sub.2 -isoxazol-3-yl
185 2-thiazolyl
186 5-NO.sub.2 -thiazol-2-yl
187 5-NO.sub.2 -imidazol-4-yl
188 4-pyrrazolyl
189 3,5-Me.sub.2 -pyrrazol-4-yl
190 5-NO.sub.2 -imidazol-4-yl
191 3-(4-Cl-phenyl)-isoxazol-5-yl
192 4-chloro-3-(3-chlorophenyl)-
isoxazol-5-yl
193 5-(4-methylphenyl)-1,3,4-
oxadiazol-2-yl
194 5-phenyl-1,3,4-thiadiazol-2-yl
195 3-(4-chlorophenyl)-1,2,4-
oxadiazol-5-yl
196 3-isopropyl-isoxazol-5-yl
197 5-(4-F-phenyl)-isoxazol-3-yl
198 4-ethyl-5-phenyl-isoxazol-3-yl
199 4-chloro-5-(3-Cl-phenyl)-
isooxazol-3-yl
200 CH.sub.2 Br
201 CH.sub.2 Cl
202 CH.sub.2 I
______________________________________
TABLE 4
______________________________________
##STR25##
phys. data
(m.p. [°C.]);
IR [cm.sup.-1 ];
No. R .sup.1 H-NMR [δ scale]
______________________________________
1 H 2.99; 3.98 (Me);
3.13 (H); 6.80
(NH); 7.21-7.58
(aryl)
2 SiMe.sub.3
3 SnMe.sub.3
4 I
5 CN
6 CH.sub.2 CH.sub.3
7 n-C.sub.3 H.sub.7
8 i-C.sub.3 H.sub.7
9 n-C.sub.4 H.sub.9
10 i-C.sub.4 H.sub.9
11 s-C.sub.4 H.sub.9
12 t-C.sub.4 H.sub.9
13 n-C.sub.5 H.sub.11
14 n-C.sub.6 H.sub.13
15 n-C.sub.7 H.sub.15
16 n-C.sub.8 H.sub.17
17 n-C.sub.9 H.sub.19
18 n-C.sub.10 H.sub.21
19 cyclopropyl
20 1-methyl-cycloprop-1-yl
21 cyclobutyl
22 cyclopentyl
23 cyclohexyl
24 cyclohex-1-en-1-yl
25 methoxymethyl
26 ethoxymethyl
27 phenoxymethyl
28 benzyloxymethyl
29 phenylmethyl
30 morpholino-N-methyl
31 phenylthiomethyl
32 2-methyl-phenyl 128-129° C.
33 3-methyl-phenyl
34 4-methyl-phenyl
35 2-chloro-phenyl
36 3-chloro-phenyl
37 4-chloro-phenyl
38 2-bromo-phenyl
39 3-bromo-phenyl
40 3-bromo-phenyl
41 2-fluorophenyl
42 3-fluorophenyl
43 4-fluorophenyl
44 2-iodo-phenyl
45 3-iodo-phenyl
46 4-iodo-phenyl
47 2-methoxy-phenyl
48 3-methoxy-phenyl
49 4-methoxy-phenyl
50 2-ethoxy-phenyl
51 3-ethoxy-phenyl
52 4-ethoxy-phenyl
53 2-n-propoxy-phenyl
54 3-n-propoxy-phenyl
55 4-n-propoxy-phenyl
56 2-i-propoxy-phenyl
57 3-i-propoxy-phenyl
58 4-i-propoxy-phenyl
59 2-n-butoxy-phenyl
60 3-n-butoxy-phenyl
61 4-n-butoxy-phenyl
62 2-sec.-butoxy-phenyl
63 3-sec.-butoxy-phenyl
64 4-sec.-butoxy-phenyl
65 2-iso-butoxy-phenyl
66 3-iso-butoxy-phenyl
67 4-iso-butoxy-phenyl
68 2-tert.-butoxyphenyl
69 3-tert.-butoxyphenyl
70 4-tert.-butoxyphenyl
71 2-ethyl-phenyl
72 3-ethyl-phenyl
73 4-ethyl-phenyl
74 2-n-propyl-phenyl
75 3-n-propyl-phenyl
76 4-n-propyl-phenyl
77 2-i-propyl-phenyl
78 3-i-propyl-phenyl
79 4-i-propyl-phenyl
80 2-n-butylphenyl
81 3-n-butylphenyl
82 4-n-butylphenyl
83 2-iso-butyl-phenyl
84 3-iso-butyl-phenyl
85 4-iso-butyl-phenyl
86 2-sec.-butylphenyl
87 3-sec.-butylphenyl
88 4-sec.-butylphenyl
89 2-tert.-butylphenyl
90 3-tert.-butylphenyl
91 4-tert.-butylphenyl
92 2-NO.sub.2 -phenyl
93 3-NO.sub.2 -phenyl
94 4-NO.sub.2 -phenyl
95 2-CF.sub.3 -phenyl
96 3-CF.sub.3 -phenyl 139-144° C.
97 4-CF.sub.3 -phenyl
98 2-CN-phenyl
99 3-CN-phenyl
100 4-CN-phenyl
101 2-(CH.sub.2 CN)-phenyl 147-151° C.
102 3-(CH.sub.2 C N)-phenyl
103 4-(CH.sub.2 CN)-phenyl
104 2-CH.sub.3 CO-phenyl
105 3-CH.sub.3 CO-phenyl
106 4-CH.sub.3 CO-phenyl
107 2-CHO-phenyl
108 3-CHO-phenyl
109 4-CHO-phenyl
110 2-NMe.sub.2 -phenyl
111 3-NMe.sub.2 -phenyl
112 4-NMe.sub.2 -phenyl
113 2-CO.sub.2 Me-phenyl
114 3-CO.sub.2 Me-phenyl
115 4-CO.sub.2 Me-phenyl
116 2-CO.sub.2 Et-phenyl
117 3-CO.sub.2 Et-phenyl
118 4-CO.sub.2 Et-phenyl
119 2-OCF.sub.3 -phenyl
120 3-OCF.sub.3 -phenyl
121 4-OCF.sub.3 -phenyl
122 2-phenyl-phenyl
123 3-phenyl-phenyl
124 4-phenyl-phenyl
125 2-phenoxy-phenyl
126 3-phenoxy-phenyl
127 4-phenoxy-phenyl
128 3,4-OCH.sub.2 O-phenyl
129 3,4-OCH.sub.2 CH.sub.2 -phenyl
130 3,4,5-(OCH.sub.3).sub.3 -phenyl
131 3,4-(OCH.sub.3).sub.2 -phenyl
132 2,3-Me.sub.2 -phenyl
133 2,4-Me.sub.2 -phenyl
134 2,5-Me.sub.2 -phenyl
135 2,6-Me.sub.2 -phenyl
136 3,4-Me.sub.2 -phenyl
137 3,5-Me.sub.2 -phenyl
138 2,4,6-Me.sub.3 -phenyl
139 2,3-Cl.sub.2 -phenyl 130-132° C.
140 2,4-Cl.sub.2 -phenyl 143-145° C.
141 2,5-Cl.sub.2 -phenyl 134-137° C.
142 2,6-Cl.sub.2 -phenyl
143 3,4-Cl.sub.2 -phenyl 147-150° C.
144 3,5-Cl.sub.2 -phenyl 159-163° C.
145 2-methyl, 5-NO.sub.2 -phenyl
146 2-methyl, 3-NO.sub.2 -phenyl
147 2-methyl, 4-F-phenyl
148 4-methyl, 3-F-phenyl
149 2,6-Cl.sub.2, 4-NO.sub.2 -phenyl
150 2-NO.sub.2, 4-Cl-phenyl
192° C.
151 2-Cl, 5-CF.sub.3 -phenyl
152 4-Cl, 3-CF.sub.3 -phenyl
153 2-methyl, 4-CH.sub.3 CO-phenyl
154 2-methyl, 5-CH.sub.3 CO-phenyl
155 2,5-Me.sub.2, 4-CH.sub.3 CO-phenyl
156 2-Me, 4-methoximinomethyl-phenyl
136-140° C.
157 2-Me, 5-methoximinomethyl-phenyl
2,12; 2,45; 2,93;
3,96; 3,99 (Me);
6,79 (NH);
7,18-7,71 (Aryl)
158 2,5-Me.sub.2, 4-methoximinomethyl-phenyl
159 2-Me, 4-ethoximinomethyl-phenyl
160 2-Me, 4-n-propoximinomethyl-phenyl
161 2-Me, 4-i-propoximinomethyl-phenyl
162 2-Me, 4-n-butoximinomethyl-phenyl
163 2-Me, 5-ethoximinomethyl-phenyl
164 2,5-Me.sub.2, 4-ethoximinomethylphenyl
165 3-(5-phenyl-1,3,4-oxadiazol-2-yl)-
phenyl
166 3-(5-naphthyl-1,3,4-oxa-
diazol-2-yl)-phenyl
167 2-pyridyl
168 3-pyridyl
169 4-pyridyl
170 5-methyl-2-pyridyl
171 6-methyl-2-pyridyl
172 quinolin-3-yl
173 2,8(CF.sub. 3).sub.2 -quinolin-4-yl
174 isoquinolin-4-yl
175 thien-2-yl
176 thien-3-yl
177 2-chloro-thien-3-yl
178 2-chloro-thien-4-yl
179 3-chloro-thien-2-yl
180 2-chloro-thien-5-yl
181 2,5-Cl.sub.2 -thien-3-yl
182 3-furyl
183 2-(isoxazol-3-yl)-thien-5-yl
184 2-cyano-thien-3-yl
185 3-Me-thien-2-yl
186 2-NO.sub.2 -thien-5-yl
187 3-benzothienyl
188 3,5-Me.sub.2 -isoxazol-3-yl
189 2-Thiazolyl
190 5-NO.sub.2 -thiazol-2-yl
191 5-NO.sub.2 -imidazol-4-yl
192 4-pyrrazolyl
193 3,5-Me.sub.2 -pyrrazol-4-yl
194 3-(4-Cl-phenyl)-isoxazol-5-yl
195 4-chloro-3-(3-chlorophenyl)-
isoxazol-5-yl
196 5-(4-methylphenyl)-1,3,4-
oxadiazol-2-yl
197 5-phenyl-1,3,4-thiadiazol-2-yl
198 3-(4-chlorophenyl)-1,2,4-
oxadiazol-5-yl
199 3-isopropyl-isoxazol-5-yl
200 5-(4-F-phenyl)-isoxazol-3-yl
201 4-ethyl-5-phenyl-isoxazol-3-yl
202 4-chloro-5-(3-Cl-phenyl)-
isoxazol-3-yl
203 CH.sub.2 Br
204 CH.sub.2 Cl
205 CH.sub.2 I
206 1-naphthyl
207 2-naphthyl 155-158° C.
208 6-methoxy-naphth-2-yl
209 CHCH-phenyl 109-112° C.
______________________________________
TABLE 5
______________________________________
##STR26##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.18 .sup.1 H-NMR [δ scale]
______________________________________
1 OH
2 O-methyl
3 O-ethyl
4 O-(n-propyl)
5 O-(i-propyl)
6 O-(n-butyl)
7 O-(i-butyl)
8 O-(s-butyl)
9 O-(tert.-butyl)
10 O-benzyl
11 O-(2-methylbenzyl)
12 O-(3-methylbenzyl)
13 O-(4-methylbenzyl)
14 O-(2-Cl-benzyl)
15 O-(3-Cl-benzyl)
16 O-(4-Cl-benzyl)
17 methyl
18 ethyl
19 n-propyl
20 i-propyl
21 n-butyl
22 i-butyl
23 s-butyl
24 tert.-butyl
25 benzyl
26 phenyl
27 2-Me-phenyl
28 3-Me-phenyl
29 4-Me-phenyl
30 2-F-phenyl
31 3-F-phenyl
32 4-F-phenyl
33 2-Cl-phenyl
34 3-Cl-phenyl
35 4-Cl-phenyl
36 2-Br-phenyl
37 3-Br-phenyl
38 4-Br-phenyl
39 2-I-phenyl
40 3-I-phenyl
41 4-I-phenyl
42 2-CF.sub.3 -phenyl
43 3-CF.sub.3 -phenyl
44 4-CF.sub.3 -phenyl
45 2-OCH.sub.3 -phenyl
46 3-OCH.sub.3 -phenyl
47 4-OCH.sub.3 -phenyl
48 2-CN-phenyl
49 3-CN-phenyl
50 4-CN-phenyl
51 2-NO.sub.2 -phenyl
52 3-NO.sub.2 -phenyl
53 4-NO.sub.2 -phenyl
54 2-OCF.sub.3 -phenyl
55 3-OCF.sub.3 -phenyl
56 4-OCF.sub.3 -phenyl
57 2-CCl.sub.3 -phenyl
58 3-CCl.sub.3 -phenyl
59 4-CCl.sub.3 -phenyl
60 2-NMe.sub.2 -phenyl
61 3-NMe.sub.2 -phenyl
62 4-NMe.sub.2 -phenyl
63 2-tert.-butylphenyl
64 3-tert.-butylphenyl
65 4-tert.-butylphenyl
66 2-tert.-butoxyphenyl
67 3-tert.-butoxyphenyl
68 4-tert.-butoxyphenyl
69 2-phenylphenyl
70 3-phenylphenyl
71 4-phenylphenyl
72 2-phenoxyphenyl
73 3-phenoxyphenyl
74 4-phenoxyphenyl
75 1-naphthyl
76 2-naphthyl
77 2,3-Me.sub.2 -phenyl
78 2,4-Me.sub.2 -phenyl
79 2,5-Me.sub.2 -phenyl
80 2,6-Me.sub.2 -phenyl
81 3,4-Me.sub.2 -phenyl
82 3,5-Me.sub.2 -phenyl
83 2,4,6-Me.sub.3 -phenyl
84 2,3-Cl.sub.2 -phenyl
85 2,4-Cl.sub.2 -phenyl
86 2,5-Cl.sub.2 -phenyl
87 2,6-Cl.sub.2 -phenyl
88 3,4-Cl.sub.2 -phenyl
89 3,5-Cl.sub.2 -phenyl
90 2-pyridyl
91 3-pyridyl
92 4-pyridyl
93 2-furyl
94 3-furyl
95 2-(5-NO.sub.2 -furyl)
96 2-thienyl
97 2-(5-Cl-thienyl)
98 2-(3-Cl-thienyl)
99 3-(thienyl)
100 2-benzofuranyl
101 2-benzothienyl
102 5-isoxazolyl
103 3-(2-Cl-pyridyl)
104 3-(6-Cl-pyridyl)
105 4-(2,6-Cl.sub.2 -pyridyl)
106 3-(5,6-Cl.sub.2 -pyridyl)
107 3-(2-phenoxypyridyl)
______________________________________
TABLE 6
______________________________________
##STR27##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.18 .sup.1 H-NMR [δ scale]
______________________________________
1 OH
2 O-methyl
3 O-ethyl
4 O-(n-propyl)
5 O-(i-propyl)
6 O-(n-butyl)
7 O-(i-butyl)
8 O-(s-butyl)
9 O-(tert.-butyl)
10 O-benzyl
11 O-(2-methylbenzyl)
12 O-(3-methylbenzyl)
13 O-(4-methylbenzyl)
14 O-(2-Cl-benzyl)
15 O-(3-Cl-benzyl)
16 O-(4-Cl-benzyl)
17 methyl
18 ethyl
19 n-propyl
20 i-propyl
21 n-butyl
22 i-butyl
23 s-butyl
24 tert.-butyl
25 benzyl
26 phenyl 89-94° C.
27 2-Me-phenyl 95-98° C.
28 3-Me-phenyl 90-92° C.
29 4-Me-phenyl 103-112° C.
30 2-F-phenyl
31 3-F-phenyl
32 4-F-phenyl
33 2-Cl-phenyl 88-93° C.
34 3-Cl-phenyl 97-102° C.
35 4-Cl-phenyl 3.87, 4.07 (OCH.sub.3), 7.35-
8.11 ppm (8H).
36 2-Br-phenyl
37 3-Br-phenyl
38 4-Br-phenyl 98-104° C.
39 2-I-phenyl
40 3-I-phenyl
41 4-I-phenyl
42 2-CF.sub.3 -phenyl
2.82, 4.03 (OCH.sub.3), 7.34-
8.11 ppm (8H).
43 3-CF.sub.3 -phenyl
88-90° C.
44 4-CF.sub.3 -phenyl
3.87, 4.07 (OCH.sub.3), 7.35-
8.28 ppm (8H).
45 2-OCH.sub.3 -phenyl
46 3-OCH.sub.3 -phenyl
47 4-OCH.sub.3 -phenyl
48 2-CN-phenyl
49 3-CN-phenyl
50 4-CN-phenyl
51 2-NO.sub.2 -phenyl
52 3-NO.sub.2 -phenyl
53 4-NO.sub.2 -phenyl
54 2-OCF.sub.3 -phenyl
55 3-OCF.sub.3 -phenyl
56 4-OCF.sub.3 -phenyl
57 2-CCl.sub.3 -phenyl
58 3-CCl.sub.3 -phenyl
59 4-CCl.sub. 3 -phenyl
60 2-NMe.sub.2 -phenyl
61 3-NMe.sub.2 -phenyl
62 4-NMe.sub.2 -phenyl
63 2-tert.-butylphenyl
64 3-tert.-butylphenyl
65 4-tert.-butylphenyl
66 2-tert.-butoxyphenyl
67 3-tert.-butoxyphenyl
68 4-tert.-butoxyphenyl
69 2-phenylphenyl
70 3-phenylphenyl
71 4-phenylphenyl
72 2-phenoxyphenyl
73 3-phenoxyphenyl
74 4-phenoxyphenyl
75 1-naphthyl
76 2-naphthyl
77 2,3-Me.sub.2 -phenyl
78 2,4-Me.sub.2 -phenyl
79 2,5-Me.sub.2 -phenyl
80 2,6-Me.sub.2 -phenyl
81 3,4-Me.sub.2 -phenyl
82 3,5-Me.sub.2 -phenyl
83 2,4,6-Me.sub.3 -phenyl
84 2,3-Cl.sub.2 -phenyl
85 2,4-Cl.sub.2 -phenyl
107-112° C.
86 2,5-Cl.sub.2 -phenyl
87 2,6-Cl.sub.2 -phenyl
88 3,4-Cl.sub.2 -phenyl
89 3,5-Cl.sub.2 -phenyl
152-157° C.
90 2-pyridyl
91 3-pyridyl
92 4-pyridyl
93 2-furyl
94 3-furyl
95 2-(5-NO.sub.2 -furyl)
96 2-thienyl
97 2-(5-Cl-thienyl)
98 2-(3-Cl-thienyl)
99 3-(thienyl)
100 2-benzofuranyl
101 2-benzothienyl
102 5-isoxazolyl
103 3-(2-Cl-pyridyl)
104 3-(6-Cl-pyridyl)
105 4-(2,6-Cl.sub.2 -pyridyl)
106 3-(5,6-Cl.sub.2 -pyridyl)
107 3-(2-phenoxypyridyl)
______________________________________
TABLE 7
______________________________________
##STR28##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.18 .sup.1 H-NMR [δ scale]
______________________________________
1 OH
2 O-methyl
3 O-ethyl
4 O-(n-propyl)
5 O-(i-propyl)
6 O-(n-butyl)
7 O-(i-butyl)
8 O-(s-butyl)
9 O-(tert.-butyl)
10 O-benzyl
11 O-(2-methylbenzyl)
12 O-(3-methylbenzyl)
13 O-(4-methylbenzyl)
14 O-(2-Cl-benzyl)
15 O-(3-Cl-benzyl)
16 O-(4-Cl-benzyl)
17 methyl
18 ethyl
19 n-propyl
20 i-propyl
21 n-butyl
22 i-butyl
23 s-butyl
24 tert.-butyl
25 benzyl
26 phenyl
27 2-Me-phenyl
28 3-Me-phenyl
29 4-Me-phenyl
30 2-F-phenyl
31 3-F-phenyl
32 4-F-phenyl
33 2-Cl-phenyl
34 3-Cl-phenyl
35 4-Cl-phenyl
36 2-Br-phenyl
37 3-Br-phenyl
38 4-Br-phenyl
39 2-I-phenyl
40 3-I-phenyl
41 4-I-phenyl
42 2-CF.sub.3 -phenyl
43 3-CF.sub.3 -phenyl
44 4-CF.sub.3 -phenyl
45 2-OCH.sub.3 -phenyl
46 3-OCH.sub.3 -phenyl
47 4-OCH.sub.3 -phenyl
48 2-CN-phenyl
49 3-CN-phenyl
50 4-CN-phenyl
51 2-NO.sub.2 -phenyl
52 3-NO.sub.2 -phenyl
53 4-NO.sub.2 -phenyl
54 2-OCF.sub.3 -phenyl
55 3-OCF.sub.3 -phenyl
56 4-OCF.sub.3 -phenyl
57 2-CCl.sub.3 -phenyl
58 3-CCl.sub.3 -phenyl
59 4-CCl.sub.3 -phenyl
60 2-NMe.sub.2 -phenyl
61 3-NMe.sub.2 -phenyl
62 4-NMe.sub.2 -phenyl
63 2-tert.-butylphenyl
64 3-tert.-butylphenyl
65 4-tert.-butylphenyl
66 2-tert.-butoxyphenyl
67 3-tert.-butoxyphenyl
68 4-tert.-butoxyphenyl
69 2-phenylphenyl
70 3-phenylphenyl
71 4-phenylphenyl
72 2-phenoxyphenyl
73 3-phenoxyphenyl
74 4-phenoxyphenyl
75 1-naphthyl
76 2-naphthyl
77 2,3-Me.sub.2 -phenyl
78 2,4-Me.sub.2 -phenyl
79 2,5-Me.sub.2 -phenyl
80 2,6-Me.sub.2 -phenyl
81 3,4-Me.sub.2 -phenyl
82 3,5-Me.sub.2 -phenyl
83 2,4,6-Me.sub.3 -phenyl
84 2,3-Cl.sub.2 -phenyl
85 2,4-Cl.sub.2 -phenyl
86 2,5-Cl.sub.2 -phenyl
87 2,6-Cl.sub.2 -phenyl
88 3,4-Cl.sub.2 -phenyl
89 3,5-Cl.sub.2 -phenyl
90 2-pyridyl
91 3-pyridyl
92 4-pyridyl
93 2-furyl
94 3-furyl
95 2-(5-NO.sub.2 -furyl)
96 2-thienyl
97 2-(5-Cl-thienyl)
98 2-(3-Cl-thienyl)
99 3-(thienyl)
100 2-benzofuranyl
101 2-benzothienyl
102 5-isoxazolyl
103 3-(2-Cl-pyridyl)
104 3-(6-Cl-pyridyl)
105 4-(2,6-Cl.sub.2 -pyridyl)
106 3-(5,6-Cl.sub.2 -pyridyl)
107 3-(2-phenoxypyridyl)
______________________________________
TABLE 8
______________________________________
##STR29##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.18 .sup.1 H-NMR [δ scale]
______________________________________
1 OH
2 O-methyl
3 O-ethyl
4 O-(n-propyl)
5 O-(i-propyl)
6 O-(n-butyl)
7 O-(i-butyl)
8 O-(s-butyl)
9 O-(tert.-butyl)
10 O-benzyl
11 O-(2-methylbenzyl)
12 O-(3-methylbenzyl)
13 O-(4-methylbenzyl)
14 O-(2-Cl-benzyl)
15 O-(3-Cl-benzyl)
16 O-(4-Cl-benzyl)
17 methyl
18 ethyl
19 n-propyl
20 i-propyl
21 n-butyl
22 i-butyl
23 s-butyl
24 tert.-butyl
25 benzyl
26 phenyl
27 2-Me-phenyl
28 3-Me-phenyl
29 4-Me-phenyl
30 2-F-phenyl
31 3-F-phenyl
32 4-F-phenyl
33 2-Cl-phenyl
34 3-Cl-phenyl
35 4-Cl-phenyl
36 2-Br-phenyl
37 3-Br-phenyl
38 4-Br-phenyl
39 2-I-phenyl
40 3-I-phenyl
41 4-I-phenyl
42 2-CF.sub.3 -phenyl
43 3-CF.sub.3 -phenyl
44 4-CF.sub.3 -phenyl
45 2-OCH.sub.3 -phenyl
46 3-OCH.sub.3 -phenyl
47 4-OCH.sub.3 -phenyl
48 2-CN-phenyl
49 3-CN-phenyl
50 4-CN-phenyl
51 2-NO.sub.2 -phenyl
52 3-NO.sub.2 -phenyl
53 4-NO.sub.2 -phenyl
54 2-OCF.sub.3 -phenyl
55 3-OCF.sub.3 -phenyl
56 4-OCF.sub.3 -phenyl
57 2-CCl.sub.3 -phenyl
58 3-CCl.sub.3 -phenyl
59 4-CCl.sub.3 -phenyl
60 2-NMe.sub.2 -phenyl
61 3-NMe.sub.2 -phenyl
62 4-NMe.sub.2 -phenyl
63 2-tert.-butylphenyl
64 3-tert.-butylphenyl
65 4-tert.-butylphenyl
66 2-tert.-butoxyphenyl
67 3-tert.-butoxyphenyl
68 4-tert.-butoxyphenyl
69 2-phenylphenyl
70 3-phenylphenyl
71 4-phenylphenyl
72 2-phenoxyphenyl
73 3-phenoxyphenyl
74 4-phenoxyphenyl
75 1-naphthyl
76 2-naphthyl
77 2,3-Me.sub.2 -phenyl
78 2,4-Me.sub.2 -phenyl
79 2,5-Me.sub.2 -phenyl
80 2,6-Me.sub.2 -phenyl
81 3,4-Me.sub.2 -phenyl
82 3,5-Me.sub.2 -phenyl
83 2,4,6-Me.sub.3 -phenyl
84 2,3-Cl.sub.2 -phenyl
85 2,4-Cl.sub.2 -phenyl
86 2,5-Cl.sub.2 -phenyl
87 2,6-Cl.sub.2 -phenyl
88 3,4-Cl.sub.2 -phenyl
89 3,5-Cl.sub.2 -phenyl
90 2-pyridyl
91 3-pyridyl
92 4-pyridyl
93 2-furyl
94 3-furyl
95 2-(5-NO.sub.2 -furyl)
96 2-thienyl
97 2-(5-Cl-thienyl)
98 2-(3-Cl-thienyl)
99 3-(thienyl)
100 2-benzofuranyl
101 2-benzothienyl
102 5-isoxazolyl
103 3-(2-Cl-pyridyl)
104 3-(6-Cl-pyridyl)
105 4-(2,6-Cl.sub.2 -pyridyl)
106 3-(5,6-Cl.sub.2 -pyridyl)
107 3-(2-phenoxypyridyl)
______________________________________
TABLE 9
______________________________________
##STR30##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.20 .sup.1 H-NMR [δ scale]
______________________________________
1 methyl
2 ethyl
3 n-propyl
4 i-propyl
5 n-butyl
6 i-butyl
7 s-butyl
8 tert.-butyl
9 benzyl
10 phenyl 3.81; 4.04; 4.12 (CH.sub.3);
7.28-7.88 ppm (9H)
11 2-Me-phenyl
12 3-Me-phenyl 2.42; 3.81, 4.05; 4.12 (CH.sub.3);
7.17-7.71 ppm (8H).
13 4-Me-phenyl 2.38; 3.82; 4.05; 4.11 (CH.sub.3);
7.18-7.75 ppm (8H).
14 2-F-phenyl
15 3-F-phenyl
16 4-F-phenyl
17 2-Cl-phenyl 3.76; 4.00; 4.12 (CH.sub.3);
7.28-7.61 ppm (8H).
18 3-Cl-phenyl
19 4-Cl-phenyl
20 2-Br-phenyl
21 3-Br-phenyl
22 4-Br-phenyl
23 2-I-phenyl
24 3-I-phenyl
25 4-I-phenyl
26 2-CF.sub.3 -phenyl
27 3-CF.sub.3 -phenyl
3.81; 4.05; 4.15 (CH.sub.3);
7.28-8.11 ppm (8H).
28 4-CF.sub.3 -phenyl
3.82; 4.05; 4.15 (CH.sub.3);
7.30-7.98 ppm (8H).
29 2-OCH.sub.3 -phenyl
30 3-OCH.sub.3 -phenyl
31 4-OCH.sub.3 -phenyl
32 2-CN-pheny
33 3-CN-phenyl
34 4-CN-phenyl
35 2-NO.sub.2 -phenyl
36 3-NO.sub.2 -phenyl
37 4-NO.sub.2 -phenyl
38 2-OCF.sub.3 -phenyl
39 3-OCF.sub.3 -phenyl
40 4-OCF.sub.3 -phenyl
41 2-CCl.sub.3 - phenyl
42 3-CCl.sub.3 - phenyl
43 4-CCl.sub.3 - phenyl
44 2-NMe.sub.2 - phenyl
45 3-NMe.sub.2 - phenyl
46 4-NMe.sub.2 - phenyl
47 2-tert.-butylphenyl
48 3-tert.-butylphenyl
49 4-tert.-butylphenyl
50 2-tert.-butoxyphenyl
51 3-tert.-butoxyphenyl
52 4-tert.-butoxyphenyl
53 2-phenylphenyl
54 3-phenylphenyl
55 4-phenylphenyl
56 2-phenoxyphenyl
57 3-phenoxyphenyl
58 4-phenoxyphenyl
59 1-naphthyl
60 2-naphthyl
61 2,3-Me.sub.2 -phenyl
62 2,4-Me.sub.2 -phenyl
63 2,5-Me.sub.2 -phenyl
64 2,6-Me.sub.2 -phenyl
65 3,4-Me.sub.2 -phenyl
66 3,5-Me.sub.2 -phenyl
67 2,4,6-Me.sub.3 -phenyl
68 2,3-Cl.sub.2 -phenyl
69 2,4-Cl.sub.2 -phenyl
70 2,5-Cl.sub.2 -phenyl
71 2,6-Cl.sub.2 -phenyl
72 3,4-Cl.sub.2 -phenyl
73 3,5-Cl.sub.2 -phenyl
74 2-pyridyl
75 3-pyridyl
76 4-pyridyl
77 2-furyl
78 3-furyl
79 2-(5-NO.sub.2 -furyl)
80 2-thienyl
81 2-(5-Cl-thienyl)
82 2-(3-Cl-thienyl)
83 3-(thienyl)
84 2-benzofuranyl
85 2-benzothienyl
86 5-isoxazolyl
87 3-(2-Cl-pyridyl)
88 3-(6-Cl-pyridyl)
89 4-(2,6-Cl.sub.2 -pyridyl)
90 3-(5,6-Cl.sub.2 -pyridyl)
91 3-(2-phenoxypyridyl)
______________________________________
TABLE 10
______________________________________
##STR31##
phys. data
m.p. [°C.]
IR [cm.sup.-1 ]
No. R.sup.20 .sup.1 H-NMR [δ scale]
______________________________________
1 methyl
2 ethyl
3 n-propyl
4 i-propyl
5 n-butyl
6 i-butyl
7 s-butyl
8 tert.-butyl
9 benzyl
10 phenyl 2.85 (d, 3H); 3.94; 4.10
(CH.sub.3); 6.79 (NH), 7.28-
7.84 ppm (9H)
11 2-Me-phenyl
12 3-Me-phenyl
13 4-Me-phenyl
14 2-F-phenyl
15 3-F-phenyl
16 4-F-phenyl
17 2-Cl-phenyl
18 3-Cl-phenyl
19 4-Cl-phenyl
20 2-Br-phenyl
21 3-Br-phenyl
22 4-Br-phenyl
23 2-I-phenyl
24 3-I-phenyl
25 4-I-phenyl
26 2-CF.sub.3 -phenyl
27 3-CF.sub.3 -phenyl
28 4-CF.sub.3 -phenyl
29 2-OCH.sub.3 -phenyl
30 3-OCH.sub.3 -phenyl
31 4-OCH.sub.3 -phenyl
32 2-CN-phenyl
33 3-CN-phenyl
34 4-CN-phenyl
35 2-NO.sub.2 -phenyl
36 3-NO.sub.2 -phenyl
37 4-NO.sub.2 -phenyl
38 2-OCF.sub.3 -phenyl
39 3-OCF.sub.3 -phenyl
40 4-OCF.sub.3 -phenyl
41 2-CCl.sub.3 - phenyl
42 3-CCl.sub.3 - phenyl
43 4-CCl.sub.3 - phenyl
44 2-NMe.sub.2 - phenyl
45 3-NMe.sub.2 - phenyl
46 4-NMe.sub.2 - phenyl
47 2-tert.-butylphenyl
48 3-tert.-butylphenyl
49 4-tert.-butylphenyl
50 2-tert.-butoxyphenyl
51 3-tert.-butoxyphenyl
52 4-tert.-butoxyphenyl
53 2-phenylphenyl
54 3-phenylphenyl
55 4-phenylphenyl
56 2-phenoxyphenyl
57 3-phenoxyphenyl
58 4-phenoxyphenyl
59 1-naphthyl
60 2-naphthyl
61 2,3-Me.sub.2 -phenyl
62 2,4-Me.sub.2 -phenyl
63 2,5-Me.sub.2 -phenyl
64 2,6-Me.sub.2 -phenyl
65 3,4-Me.sub.2 -phenyl
66 3,5-Me.sub.2 -phenyl
67 2,4,6-Me.sub.3 -phenyl
68 2,3-Cl.sub.2 -phenyl
69 2,4-Cl.sub.2 -phenyl
70 2,5-Cl.sub.2 -phenyl
71 2,6-Cl.sub.2 -phenyl
72 3,4-Cl.sub.2 -phenyl
73 3,5-Cl.sub.2 -phenyl
74 2-pyridyl
75 3-pyridyl
76 4-pyridyl
77 2-furyl
78 3-furyl
79 2-(5-NO.sub.2 -furyl)
80 2-thienyl
81 2-(5-Cl-thienyl)
82 2-(3-Cl-thienyl)
83 3-(thienyl)
84 2-benzofuranyl
85 2-benzothienyl
86 5-isoxazolyl
87 3-(2-Cl-pyridyl)
88 3-(6-Cl-pyridyl)
89 4-(2,6-Cl.sub.2 -pyridyl)
90 3-(5,6-Cl.sub.2 -pyridyl)
91 3-(2-phenoxypyridyl)
______________________________________
The novel compounds are suitable as fungicides.
The fungicidal compounds according to the invention, or agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
Normally, the plants are sprayed or dusted with the active ingredients or the seeds of the plants are treated with the active ingredients.
The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
Examples of such formulations are given below.
I. A solution of 90 parts by weight of compound no. 1 from Table 2 and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for application in the form of very fine drops.
II. A mixture of 20 parts by weight of compound no. 24 from Table 2, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, a dispersion is obtained.
III. An aqueous dispersion of 20 parts by weight of compound no. 25 from Table 2, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
IV. An aqueous dispersion of 20 parts by weight of compound no. 26 from Table 2, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
V. A hammer-milled mixture of 80 parts by weight of compound no. 31 from Table 2, 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.
VI. An intimate mixture of 3 parts by weight of compound no. 33 from Table 2 and 97 parts by weight of particulate kaolin. The dust contains 3 wt % of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 34 from Table 2, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.
VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 35 from Table 2, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.
IX. A stable oily dispersion of 20 parts by weight of compound no. 42 from Table 2, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
The novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a remarkably high systemic mobility and action after application to the soil and particularly to foliage.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The compounds are applied by treating the seeds, plants, materials or soil to be protected against fungus attack with a fungicidally effective amount of the active ingredients.
The compounds may be applied before or after infection of the materials, plants or seeds by the fungi.
The compounds I are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
Podosphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
Rhizoctonia solani in cotton,
Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples,
H elminthosporium species in cereals,
Septoria nodorum in wheat,
Botrytis cinerea (gray mold) in strawberries and grapes,
Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes,
Fusarium and Verticillium species in various plants,
Plasmopara viticola in grapes,
Alternaria species in fruit and vegetables.
The novel compounds may also be used for protecting materials (timber), for example against Paecilomyces variotii.
The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient.
The application rates depend on the type of effect desired, but are generally from 0.02 to 3 kg of active ingredient per hectare.
When the active ingredients are used for treating seed, application rates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are generally required.
When the agents according to the invention are used as fungicides, they may be employed together with other active ingredients, e.g., herbicides, insecticides, growth regulators, other fungicides and fertilizers.
When admixed with other fungicides, the spectrum of fungicidal action is in many instances increased.
In the active ingredients used for comparison purposes, U, V and W=H, A=CH3 ON═, B=CH3 O and R=phenyl (compound 1), R=2-chlorophenyl (compound B) , and R=4-CF3 -phenyl (compound C). All of these compounds are known from EP 253 213.
Action on cucumber mildew
Young cucumber plants of the "Chinesische Schlange" variety were sprayed to runoff at the two-leaf stage with an aqueous spray liquor. The next day these plants were sprayed with an aqueous conidial suspension of cucumber mildew (Erysiphe cichoracearum and Sphaerotheca fuliginea), and kept in the greenhouse at 20° to 22° C. and a relative humidity of 70 to 80%. The extent of fungus spread was determined 21 days after application of the active ingredients.
The results show that the active ingredients from Table 2, no. 33 (2,33), 2,43; 2,148 and 2,166 have, when applied as a spray liquor containing 63 ppm of active ingredient, a better fungicidal action (10% leaf attack) than prior art comparative active ingredients A, B and C (45% leaf attack).
Action on Botrytis cinerea in paprika pods (fruit test)
Slices of green paprika pods were sprayed to runoff with aqueous formulations containing 80% of active ingredient and 20% of emulsifier. Two hours after the sprayed-on layer had dried, the slices were inoculated with a spore suspension of Botrytis cinerea containing 1.7×106 spores per ml of a 2% biomalt solution. The inoculated slices were then incubated in moist chambers for 4 days at 18° C. The extent of Botrytis spread on the slices was then assessed visually.
The results show that active ingredients 2,25; 2,35; 2,166 and 2,179, when applied as spray liquors containing 500 ppm of active ingredient, have a better fungicidal action (10% attack) than prior art comparative active ingredient A (30% attack).
Action on Plasmopara viticola
Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24° C. and then in a greenhouse for 5 days at from 20° to 30° C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1,195; 2,25; 2,35; 2,43; 2,86; 2,88; 2,92; 2,94; 2,95 and 2,148, when applied as spray liquors containing 16 ppm of active ingredient, have a better fungicidal action (5% leaf attack) than prior art comparative active ingredient C (35% leaf attack).
Claims (10)
1. An acetylene derivative of the formula I ##STR32## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C1 -C4 -alkyl or C1 -C4 -alkoxy,
A is C1 -C4 -alkoximino,
B is OH or C1 -C4 -alkoxy and
R is hydrogen, halogen, cyano, CF3, straight-chain or branched C1 -C10 -alkyl, C3 -C6 -cycloalkyl, unsubstituted or substituted aryl, halo-C1 -C4 -alkyl, C2 -C6 -alkenyl, C2 -C4 -alkynyl, unsubstituted or substituted aryl-C1 -C4 -alkyl, unsubstituted or substituted aryl-C2 -C4 -alkenyl, unsubstituted or substituted arylethynyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, unsubstituted or substituted aryloxy-C1 -C4 -alkyl, unsubstituted or substituted arylamino-C1 -C4 -alkyl, unsubstituted or substituted arylthiomethyl, C(O)R1, C(O)NR2 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, C(OR)R18 or C(═N--OR19)R20 and
R1 --R17, R19 and R20 are identical or different and are each hydrogen, C1 -C4 -alkyl, unsubstituted or substituted aryl or unsubstituted or substituted arylalkyl,
R18 is OH, C1 -C4 -alkoxy or unsubstituted or substituted aryl-C1 -C4 -alkoxy,
the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkyl, C1 -C4 -haloalkoxy, C1 -C4 -alkoximino-C1 -C4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, C3 -C6 -cycloalkyl, C1 -C4 -dialkylamino, CO2 Me, CO2 Et, formyl or acyl and Me is methyl and Et is ethyl, with the exception of the following individual compounds of the formula I where
A=CHOCH3, B=OCH3 and R=phenyl
A=CHSCH3, B=OCH3 and R=phenyl
A=CHCH3, B=OCH3, and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=OCH3 and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=NHCH3, R=CH3, phenyl,
A=CHOCH3, B=NHCH3, R=CH3, phenyl and
A=CHSCH3, B=NHCH3, R=phenyl.
2. An acetylene derivative of the formula III ##STR33## where R is a defined in claim 1.
3. An acetylene derivative of the formula VII ##STR34## where A and B are as defined in claim 1.
4. A fungicide containing an inert carrier and a fungicidally effective amount of an acetylene derivative of the formula I ##STR35## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C1 -C4 -alkyl or C1 -C4 -alkoxy,
A is C1 -C4 -alkoximino,
B is OH or C1 -C4 -alkoxy and
R is hydrogen, halogen, cyano, CF3, straight-chain or branched C1 -C10 -alkyl, C3 --C6 -cycloalkyl, unsubstituted or substituted aryl, halo-C1 -C4 -alkyl, C2 -C6 -alkenyl, C2 -C4 -alkynyl, unsubstituted or substituted aryl-C1 -C4 -alkyl, unsubstituted or substituted aryl-C2 -C4 -alkenyl, unsubstituted or substituted arylethynyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, unsubstituted or substituted aryloxy-C1 -C4 -alkyl, unsubstituted or substituted arylamino-C1 -C4 -alkyl, unsubstituted or substituted arylthiomethyl, C(O)R1, C(O)NR2 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, C(OR)R18 or C(═N--OR19)R20 and
R1 -R17, R19 and R20 are identical or different and are each hydrogen, C1 -C4 -alkyl, unsubstituted or substituted aryl or unsubstituted or substituted arylalkyl,
R18 is OH, C1 -C4 -alkoxy or unsubstituted or substituted aryl-C1 -C4 -alkoxy,
the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkyl, C1 -C4 -haloalkoxy, C1 -C4 -alkoximino-C1 -C4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, C3 -C6 -cycloalkyl, C1 -C4 -dialkylamino, CO2 Me, CO2 Et, formyl or acyl and Me is methyl and Et is ethyl, with the exception of the following individual compounds of the formula I where
A=CHOCH3, B=OCH3 and R=phenyl
A=CHSCH3, B=OCH3 and R=phenyl
A=CHCH3, B=OCH3, and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=OCH3 and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=NHCH3, R=CH3, phenyl,
A=CHOCH3, B=NHCH3, R=CH3, phenyl and
A=CHSCH3, B=NHCH3, R=phenyl.
5. A method of combatting fungi, wherein the fungi, or the materials, plants or seeds to be protected against fungus attack, or the soil are treated with a fungicidally effective amount of a compound of the formula ##STR36## where U, V and W are identical or different and are each hydrogen, halogen, nitro, cyano, C1 -C4 -alkyl or C1 -C4 -alkoxy,
A is C1 -C4 -alkoximino,
B is OH or C1 -C4 -alkoxy and
R is hydrogen, halogen, cyano, CF3, straight-chain or branched C1 -C10 -alkyl, C3 -C6 -cycloalkyl, unsubstituted or substituted aryl, halo-C1 -C4 -alkyl, C2 -C6 -alkenyl, C2 -C4 -alkynyl, unsubstituted or substituted aryl-C1 -C4 -alkyl, unsubstituted or substituted aryl-C2 -C4 -alkenyl, unsubstituted or substituted arylethynyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, unsubstituted or substituted aryloxy-C1 -C4 -alkyl, unsubstituted or substituted arylamino-C1 -C4 -alkyl, unsubstituted or substituted arylthiomethyl, C(O)R1, C(O)NR1 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, C(OR)R18 or C(═N--OR19)R20 and
R1 -R17, R19 and R20 are identical or different and are each hydrogen, C1 -C4 -alkyl, unsubstituted or substituted aryl or unsubstituted or substituted arylalkyl,
R18 is OH, C1 -C4 -alkoxy or unsubstituted or substituted aryl-C1 -C4 -alkoxy,
the term "unsubstituted or substituted" denoting, in addition to hydrogen, halogen, cyano, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, C1 -C4 -haloalkyl, C1 -C4 -haloalkoxy, C1 -C4 -alkoximino-C1 -C4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, C3 -C6 -cycloalkyl, C1 -C4 -dialkylamino, CO2 Me, CO2 Et, formyl or acyl and Me is methyl and Et is ethyl, with the exception of the following individual compounds of the formula I where
A=CHOCH3, B=OCH3 and R=phenyl
A=CHSCH3, B=OCH3 and R=phenyl
A=CHCH3, B=OCH3, and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=OCH3 and R=phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2-methylphenyl, 4-bromophenyl, 4-trifluoromethylphenyl or 4-methylphenyl,
A=NOCH3, B=NHCH3, R=CH3, phenyl,
A=CHOCH3, B=NHCH3, R=CH3, phenyl and
A=CHSCH3, B=NHCH3, R=phenyl.
6. The acetylene derivative of claim 1, wherein R is hydrogen, halogen, cyano, CF3, straight-chain or branched C1 -C10 -alkyl, C3 -C6 -cycloalkyl, halo-C1 -C4 -alkyl, C2 -C6 -alkenyl, C2 -C4 -alkynyl, unsubstituted or substituted aryl-C1 -C4 -alkyl, unsubstituted or substituted aryl-C2 -C4 -alkenyl, unsubstituted or substituted aryl-ethynyl, C1 -C4 -alkoxy-C1 -C4 -alkyl, unsubstituted or substituted aryloxy-C1 -C4 -alkyl, unsubstituted or substituted arylamino-C1 -C4 -alkyl, unsubstituted or substituted arylthiomethyl C(O)R1, C(O)NR2 R3, C(S)NR4 R5, C(O)SR6, C(S)OR7, C(S)SR8, CH(OH)R9, CH(OR10)R11, C(O)R16 or C(═N--OR19)R20.
7. The acetylene derivative of claim 2, wherein R is phenyl substituted with halogen, cyano, nitro, C1 -C4 alkoxy, C1 -C4 -haloalkyl, C1 -C4 -haloalkoxy, C1 -C4 -alkoxyimino-C1 -C4 -alkyl, aryl, aryloxy, benzyl, benzyloxy, C3 -C6 -cycloalkyl, C1 -C4 -dialkylamino, CO2 Me, CO2 Et, formyl or acyl.
8. The acetylene derivative of claim 7, wherein R is selected from the group consisting of 2,3-Me2 -phenyl, 2,4-Me2 -phenyl, 2,5-Me2 -phenyl, 2,6-Me2 -phenyl, 3,4-Me2 -phenyl, 3,5-Me2 -phenyl and 2,4,6-Me3 -phenyl.
9. The acetylene derivative of claim 2, wherein R is selected from the group consisting of 2-CN-phenyl, 3-CN-phenyl, 4-CN-phenyl, 2-(CH2 CN)-phenyl, 3-(CH2 CN)-phenyl and 4-(CH2 CN)-phenyl.
10. The acetylene derivative of claim 9, wherein R is 3-(CH2 CN)-phenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/443,460 US5686474A (en) | 1992-08-11 | 1995-05-18 | Acetylene derivatives and crop protection agents containing them |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4226557.6 | 1992-08-11 | ||
| DE4226557 | 1992-08-11 | ||
| DE4239874.6 | 1992-11-27 | ||
| DE4239874 | 1992-11-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| US08/443,460 Division US5686474A (en) | 1992-08-11 | 1995-05-18 | Acetylene derivatives and crop protection agents containing them |
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| Publication Number | Publication Date |
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| US5449809A true US5449809A (en) | 1995-09-12 |
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| US08/099,693 Expired - Fee Related US5449809A (en) | 1992-08-11 | 1993-07-30 | Acetylene derivatives and crop protection agents containing them |
| US08/443,460 Expired - Fee Related US5686474A (en) | 1992-08-11 | 1995-05-18 | Acetylene derivatives and crop protection agents containing them |
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| US (2) | US5449809A (en) |
| EP (2) | EP0718292B1 (en) |
| JP (1) | JPH06239824A (en) |
| AT (2) | ATE165352T1 (en) |
| AU (1) | AU663208B2 (en) |
| CA (1) | CA2101664A1 (en) |
| DE (2) | DE59308455D1 (en) |
| DK (1) | DK0582925T3 (en) |
| ES (1) | ES2093335T3 (en) |
| GR (1) | GR3021235T3 (en) |
| HU (1) | HUT68742A (en) |
| IL (1) | IL106473A0 (en) |
| NZ (1) | NZ248276A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686474A (en) * | 1992-08-11 | 1997-11-11 | Basf Aktiengesellschaft | Acetylene derivatives and crop protection agents containing them |
| WO2000055636A1 (en) * | 1999-03-16 | 2000-09-21 | Proteome Systems Ltd. | Method and apparatus for manipulating arrays |
| WO2013020096A2 (en) * | 2011-08-03 | 2013-02-07 | Stc.Unm | Antimicrobial materials and methods |
| US9750250B2 (en) | 2015-01-14 | 2017-09-05 | Stc.Unm | Conjugated polyelectrolytes and methods of using the same |
| US9968698B2 (en) | 2013-11-08 | 2018-05-15 | Stc. Unm | Charged singlet-oxygen sensitizers and oppositely-charged surfactants |
| US10092000B2 (en) | 2010-07-13 | 2018-10-09 | Stc.Unm | Structure, synthesis, and applications for oligo phenylene ethynylenes (OPEs) |
| WO2019083397A1 (en) | 2017-10-23 | 2019-05-02 | Общество С Ограниченной Ответственностью "Сан Системз" | Solubilization of chlorhexidine base, anitseptic composition and disinfectant composition |
| WO2019189287A1 (en) | 2018-03-29 | 2019-10-03 | 住友化学株式会社 | Alkyne compound and arthropod pest control composition containing same |
| US10533991B2 (en) | 2014-03-14 | 2020-01-14 | Stc.Unm | P-phenylene ethynylene compounds as bioactive and detection agents |
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| AU659918B2 (en) * | 1992-03-06 | 1995-06-01 | Workspace Commercial Furniture Pty Ltd | Improved height adjustment device |
| RU2146247C1 (en) * | 1994-06-10 | 2000-03-10 | Басф Акциенгезельшафт | Methods and intermediate products for preparing alpha- methoxyiminocarboxylic acid methylamides |
| FR2727408A1 (en) * | 1994-11-29 | 1996-05-31 | Roussel Uclaf | NOVEL OXIMES DERIVED FROM 7-ETHYNYL ALPHA- (OXO) 1-NAPHTHALENE ACETIC ACID, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PESTICIDES |
| DE19512886A1 (en) * | 1995-04-06 | 1996-10-10 | Bayer Ag | Substituted cycloalkenes |
| FR2751642B1 (en) * | 1996-07-24 | 1998-09-11 | Hoechst Schering Agrevo Sa | NOVEL DERIVATIVES OF BETA-METHOXY ACRYLIC ACID, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES |
| WO2008156656A2 (en) * | 2007-06-13 | 2008-12-24 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Method for making biaryl compounds, compounds made by the method, and method for their use |
| WO2014121883A1 (en) | 2013-02-07 | 2014-08-14 | Merck Patent Gmbh | Substituted acetylene derivatives and their use as positive allosteric modulators of mglur4 |
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- 1993-07-29 NZ NZ248276A patent/NZ248276A/en unknown
- 1993-07-30 US US08/099,693 patent/US5449809A/en not_active Expired - Fee Related
- 1993-07-30 CA CA002101664A patent/CA2101664A1/en not_active Abandoned
- 1993-07-31 DE DE59308455T patent/DE59308455D1/en not_active Expired - Lifetime
- 1993-07-31 DE DE59304032T patent/DE59304032D1/en not_active Expired - Lifetime
- 1993-07-31 AT AT96101050T patent/ATE165352T1/en not_active IP Right Cessation
- 1993-07-31 DK DK93112327.7T patent/DK0582925T3/en active
- 1993-07-31 AT AT93112327T patent/ATE143657T1/en not_active IP Right Cessation
- 1993-07-31 EP EP96101050A patent/EP0718292B1/en not_active Expired - Lifetime
- 1993-07-31 ES ES93112327T patent/ES2093335T3/en not_active Expired - Lifetime
- 1993-07-31 EP EP93112327A patent/EP0582925B1/en not_active Expired - Lifetime
- 1993-08-10 JP JP5198510A patent/JPH06239824A/en active Pending
- 1993-08-10 HU HU9302315A patent/HUT68742A/en unknown
- 1993-08-10 AU AU44517/93A patent/AU663208B2/en not_active Ceased
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| US5686474A (en) * | 1992-08-11 | 1997-11-11 | Basf Aktiengesellschaft | Acetylene derivatives and crop protection agents containing them |
| WO2000055636A1 (en) * | 1999-03-16 | 2000-09-21 | Proteome Systems Ltd. | Method and apparatus for manipulating arrays |
| US10092000B2 (en) | 2010-07-13 | 2018-10-09 | Stc.Unm | Structure, synthesis, and applications for oligo phenylene ethynylenes (OPEs) |
| US10750746B2 (en) | 2010-07-13 | 2020-08-25 | University Of Florida Research Foundation, Inc. | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
| US10174042B2 (en) | 2010-07-13 | 2019-01-08 | Stc.Unm | Structure, synthesis, and applications for poly (phenylene) ethynylenes (PPEs) |
| WO2013020096A3 (en) * | 2011-08-03 | 2013-05-02 | Stc.Unm | Antimicrobial materials and methods |
| US10058099B2 (en) | 2011-08-03 | 2018-08-28 | Stc.Unm | Antimicrobial materials and methods |
| US9549549B2 (en) | 2011-08-03 | 2017-01-24 | Stc.Unm | Antimicrobial materials and methods |
| WO2013020096A2 (en) * | 2011-08-03 | 2013-02-07 | Stc.Unm | Antimicrobial materials and methods |
| US9968698B2 (en) | 2013-11-08 | 2018-05-15 | Stc. Unm | Charged singlet-oxygen sensitizers and oppositely-charged surfactants |
| US10533991B2 (en) | 2014-03-14 | 2020-01-14 | Stc.Unm | P-phenylene ethynylene compounds as bioactive and detection agents |
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| US10638759B2 (en) | 2015-01-14 | 2020-05-05 | University Of Florida Research Foundation, Inc. | Conjugated polyelectrolytes and methods of using the same |
| US10772851B2 (en) | 2017-02-03 | 2020-09-15 | Aaron Kurt Neumann | Treatment and prevention of fungal infections |
| WO2019083397A1 (en) | 2017-10-23 | 2019-05-02 | Общество С Ограниченной Ответственностью "Сан Системз" | Solubilization of chlorhexidine base, anitseptic composition and disinfectant composition |
| WO2019189287A1 (en) | 2018-03-29 | 2019-10-03 | 住友化学株式会社 | Alkyne compound and arthropod pest control composition containing same |
| CN111902392A (en) * | 2018-03-29 | 2020-11-06 | 住友化学株式会社 | Alkyne compound and harmful arthropod control composition containing same |
| EP3778551A4 (en) * | 2018-03-29 | 2022-04-06 | Sumitomo Chemical Company Limited | Alkyne compound and arthropod pest control composition containing same |
| US11490619B2 (en) | 2018-03-29 | 2022-11-08 | Sumitomo Chemical Company, Limited | Alkyne compound and arthropod pest control composition containing same |
| CN111902392B (en) * | 2018-03-29 | 2023-03-31 | 住友化学株式会社 | Alkyne compound and harmful arthropod control composition containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2101664A1 (en) | 1994-02-12 |
| EP0582925A1 (en) | 1994-02-16 |
| HU9302315D0 (en) | 1993-11-29 |
| AU4451793A (en) | 1994-02-17 |
| DE59304032D1 (en) | 1996-11-07 |
| ATE143657T1 (en) | 1996-10-15 |
| US5686474A (en) | 1997-11-11 |
| EP0718292A1 (en) | 1996-06-26 |
| JPH06239824A (en) | 1994-08-30 |
| EP0582925B1 (en) | 1996-10-02 |
| GR3021235T3 (en) | 1997-01-31 |
| EP0718292B1 (en) | 1998-04-22 |
| IL106473A0 (en) | 1993-11-15 |
| NZ248276A (en) | 1995-03-28 |
| HUT68742A (en) | 1995-07-28 |
| ES2093335T3 (en) | 1996-12-16 |
| ATE165352T1 (en) | 1998-05-15 |
| DE59308455D1 (en) | 1998-05-28 |
| DK0582925T3 (en) | 1996-11-18 |
| AU663208B2 (en) | 1995-09-28 |
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